/LWR-EX-10-12

EVALUATION OF DEAMMONIFICATION PROCESS PERFORMANCE FOR SUPERNATANT TREATMENT

Zaira Hernando & Sandra Martínez

June 2010

TRITA-LWR Degree Project ISSN 1651-064X LWR-EX-10-12

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project.

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Evaluation of Deammonification process performance for supernatant treatment

© Zaira Hernando & Sandra Martínez 2010 Master of Science Thesis Water System Technology Department of Land and Water Resources Engineering Royal Institute of Technology (KTH) SE-100 44 STOCKHOLM, Sweden Reference should be written as: Hernando, Z. & Martínez, S. (2010) “Evaluation of Deammonification process performance for supernatant treatment” TRITA-LWR-EX-10-12

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S AMMANFATTNING För närvarande finns det ett ökande behov av att behandla avloppsvatten på ett hållbart sätt och striktare lagstiftning för utgående avloppsvattens kvalitet har införts i många länder. Vid konventionella avloppsverk utgör ofta avlägsnande av kväve ett kritiskt steg. En ny biologisk process för avlägsnande av ammonium ur avloppsvatten kallad anammox (Anaerobic Ammonium Oxidation) har nyligen utvecklats till en lovande möjlighet för behandling av avloppsvatten med en låg C/N-kvot. Partiell nitritation följd av anammoxprocessen synes vara ett utmärkt alternativ till traditionell nitrifikation/denitrifikation. En studie genomfördes under sex månader vid Hammarby Sjöstads forskningsstation lokaliserad i Stockholm. Drift av en-stegs process med deammonifikation skedde i två olika systemutformningar i laboratorie- och pilotskala. Studierna genomfördes med syfte att bestämma olika parametrar på processresultat. Analyser på kväveformer, alkalinitet och COD genomfördes regelbundet. Reaktorerna i laboratorieskala drevs i serie för att sedan drivas parallellt och med olika strategier med intermittent luftning. Detta resulterade i en högre effektivitet för avlägsnande av kväve. Ett starkt samband erhölls mellan konduktivitet och halt av oorganiskt kväve för inkommande och utgående flöde. Diskontinuerliga laboratorieförsök genomfördes dessutom för att bedöma bästa möjliga strategi för luftningen för partiell nitritation följd av anammoxprocessen. Halten löst syre och bildningshastigheten för nitritationen synes vara de begränsande faktorerna för anammoxreaktionen vid användning av en-stegsteknik. Aktivitetstester baserade på kvävgasbildning genomfördes för att bestämma potentiella specifika anammoxaktiviteten med syfte att jämföra hastigheten för att avskilja kväve vid deammonifikationsprocessen. Bakterieaktivitet vid olika temperaturer har även studerats.

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Evaluation of Deammonification process performance for supernatant treatment

A CKNOWLEDGMENTS This Master Thesis was carried out thanks to the Erasmus Program between the Department of Land and Water Resources Engineering, Royal Institute of Technology (KTH) in Stockholm (Sweden) and the Department of Chemical Engineering, University of Santiago de Compostela (Spain). First of all we would like to express our deepest gratitude to our supervisor Professor Elzbieta Plaza for giving us the opportunity of taking part in a very interesting research project. Thank you for your scientific guidance, suggestions and encouragement. We would like to express our gratitude to Professor Ramón Méndez Pampín from University of Santiago de Compostela, for his support and kind assistance throughout our academical career. We are grateful to Dr. Eng. Józef Trela, the leader of Deammonification project, for sharing his knowledge and for his friendliness. We would like to thank to Isaac Fernández, PhD student at the Deparment of Chemical Engineering from University of Santiago de Compostela, for introducing us in the Anammox world and providing us with lots of literature and advices. Sincere thanks to Jingjing Yang, PhD student at the Department of Land and Water Resources Engineering (KTH), for her help and patience. We really appreciate your devoting time during our stay in Stockholm. We wish you both the best in your professional career. We are especially grateful to Dr. Eng. Monika śubrowska for sharing her ideas, smile and positive influence. Monika Löwén, thank you for your help with laboratory issues and for being always friendly. Sincere thanks to Lars Bengtsson, Christian Baresel and Laryssa Sys from Hammarby Sjöstad Research Station, for collaboration and making facilities available to our research, for the small talks, good company and for create such a friendly work atmosphere. Hearty gratitude to all our close friends in Stockholm, especially to Victor Herrero, for making our life in Stockholm unforgettable and plenty of good memories. Thank you for your patience, endless support and unconditional friendship that have made us surmount successfully every obstacle during the progress of this thesis. To our boyfriends Alberto García and Alberto Eyo, for their love, encouragement, understanding and just for being always there. For our family, for their love and support. For the education they have given to us and for being always a role model. Thank you! Sandra & Zaira Stockholm, June 2010.

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“What we know is a drop of water, what we ignore is the ocean� Isaac Newton

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Evaluation of Deammonification process performance for supernatant treatment

T ABLE OF C ONTENT Sammanfattning Acknowledgments Table of Content List of tables List of figures Acronyms and abreviations Abstract 1. Introduction 1.1. 1.2. 1.3.

General background The Anammox process, a short-cut in the traditional nitrogen cycle New biological processes for nitrogen removal from wastewater

1.3.1. 1.3.2. 1.3.3. 1.3.4.

1.4.

2.

Swedish wastewater treatment development

7 9 9 10

General description Operational parameters Dissolved Oxygen pH Conductivity Temperature Oxidation Reduction Potential (ORP)

10 11 12 12 13

Aims of the Thesis Experimental Strategy and methodology

15 15 15 16 17 18 21

2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.2.5.

4.1. 4.2. 4.3. 4.4. 4.5.

Hammarby Sjรถstad Research Station (HSRS) Studies on Deammonification process Supernatant Characteristics Kaldness biofilm carriers Measurements and Analyses

4.5.1. 4.5.2. 4.5.3. 4.5.4.

5.

6 7 7 7

Characterization of Deammonification process 2.1. 2.2.

3. 4.

CANON process Oland process SHARON process Deammonification process

Physical parameters Chemical Analyses Specific Anammox Activity (SAA) tests to determine Nitrogen gas production Deammonification Efficiency

Laboratory scale Deammonification reactor 5.1.

Materials and Methods Results and discussion Conclusions

26 28 33

5.2. Study on the optimization and influence of aeration strategy on the process performance 5.2.1. 5.2.2. 5.2.3.

Materials and Methods Results and discussion Conclusions

51 51 52

Materials and methods Results and discussion

6.2.1. 6.2.2.

34 34 36 50

Batch experiments with intermittent aeration 6.1. 6.2.

21 21 22 25

25 26

Evaluation of the reactor operation

5.1.1. 5.1.2. 5.1.3.

6.

v vii xi xiii xvii xxi 1 1 1 3 6

Group I Group II

52 53

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6.3.

7.

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Conclusions

58 59 59 61

Pilot plant Deammonification reactor 7.1. 7.2.

Materials and methods Results and discussion

7.2.1. 7.2.2. 7.2.3. 7.2.4. 7.2.5. 7.2.6.

7.3.

Physical Parameters Chemical Analyses Biomass measurements Suspended Solids (SS) in supernatant Bacterial activity measurements Removal efficiency

61 64 68 68 70 73

Conclusions

73

8. General conclusions 74 9. Recomendations for future studies 75 10. References 76 Appendix I. Data of measurements and analyses from lab-scale deammonification reactors (serial system) during October 13st 2009 – November 24th 2009. I Appendix II. Data of measurements and analyses from the lab-scale deammonification reactors (parallel system) during November 27st 2009 – December 21th 2009. V Appendix III. Data of measurements and analyses from batch tests during December 1ST 2009 – December 17th 2009. XXIII Appendix IV. Data of measurements and analyses from pilot plant deammonification reactor during January 28st 2009 – April 2nd 2010. XXIX

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L IST OF TABLES Table 1. Differences between Nitrification and Denitrification processes. Table 2. Types of Anammox bacteria. Table 3. Parameters of ammonium oxidation in aerobic and anaerobic conditions. Table 4. Main factors influencing Deammonification process. Table 5. Characteristics of supernatant from Hammarby Sjöstadsverk digester. Table 6. Operational parameters of lab-scale Deammonification reactors. Table 7. Variations of physical parameters in lab-scale Deammonification reactors during the operational period Table 8. Chemical Analyses results from lab-scale Deammonification reactors during the operational period. Table 9. SAA in g N/m2d during the operational period. Table 10. SAA in g N/gVSS d during the operational period. Table 11. Total nitrogen and ammonium removal efficiency of lab-scale Deammonification reactors. Table 12. Characteristics of supernatant from Himmerfjärden WWTP. Table 13. Operational parameters of lab-scale Deammonification reactors. Table 14. DO variations of lab-scale Deammonification reactors during the aeration period. Table 15. pH variations of lab-scale Deammonification reactors during the research period. Table 16. Conductivity variations of lab-scale Deammonification reactors during the research period. Table 17. Temperature variations of lab-scale Deammonification reactors during the research period. Table 18. Redox potential variations of lab-scale Deammonification reactors during the research period. Table 19. Ammonium concentration in lab-scale Deammonification reactors during the research period. Table 20. Nitrite concentration in lab-scale Deammonification reactors during the research period. Table 21. Nitrate concentration in lab-scale Deammonification reactors during the research period.

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Table 22. Alkalinity variations in lab-scale Deammonification reactors during the research period. Table 23. Biomass developed on Kaldnes carriers. Table 24. SAA in g N/m2d during the operational period. Table 25. SAA in g N/gVSS d during the operational period. Table 26. Deammonification process activity in g N/m2 d during the operational period. Table 27. Total nitrogen removal efficiency of lab-scale Deammonification reactors. Table 28. Ammonium removal efficiency of lab-scale Deammonification reactors. Table 29. Batch experiments summary. Table 30. Chemical analysis Group I. Table 31. Aeration strategies used during batch experiments. Group II. Table 32. Chemical analyses for different aeration ratios, DO= 2 mg/L. Table 33. Chemical analyses for different aeration ratios, DO= 3 mg/L. Table 34. Chemical analyses for different aeration ratios, DO= 4 mg/L. Table 35. Characteristics of supernatant from Bromma WWTP. Table 36. Operational parameters of Pilot plant Deammonification reactor. Table 37. DO variations of Deammonification reactor during the research period. Table 38. pH variations of Deammonification reactor during the research period. Table 39. Conductivity variations of Deammonification reactor during the research period. Table 40. Temperature variations of Deammonification reactor during the research period. Table 41. Redox potential variations of Deammonification reactor during the research period. Table 42. Ammonium concentration in Deammonification reactor during the research period. Table 43. Nitrite concentration in Deammonification reactor during the research period. Table 44. Nitrate concentration in Deammonification reactor during the research period.

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Table 45. Alkalinity values in Deammonification reactor during the research period. Table 46. COD concentration in Deammonification reactor during the research period. Table 47. Biomass developed on Kaldnes carriers. Table 48. Analyses of TSS in inflow, outflow and activated sludge. Table 49. Analyses of VSS in inflow, outflow and activated sludge. Table 50. SAA in g N/m2 d measured at 35 °C and 25 °C. Table 51. SAA in g N/VSS d measured at 35 °C and 25 °C. Table 52. Deammonification activity during the operational period. Table 53. Total nitrogen and ammonium removal efficiency of the pilot plant Deammonification reactor.

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L IST OF FIGURES Fig. 1. Short-cut in nitrogen cycle using Anammox process. Fig. 2. Granules of Anammox bacteria. Fig. 3. WWTP’s in Stockholm. Fig. 4. Himmerfjärden WWTP-pilot plant for studies of Anammox process. Fig. 5. Redox potential ranges (mV) for typical wastewater processes. Fig. 6. Exaggerated ORP profile for an intermittent aeration wastewater treatment system. Fig. 7. Facilities at HSRS. Fig. 8. Main events during the experimental work at HSRS. Fig. 9. Localization of Laboratory and Pilot Plant at HSRS. Fig. 10. Compacted Kaldnes carriers with biomass attached. Fig. 11. Scheme of the chemical reactions occurring within the biofilm. Fig. 12. Kaldnes carriers with biomass attached for industrial applications. Fig. 13. Filter and Aluminum dish after ignition. Fig. 14. Relation between pH and alkalinity forms. Fig. 15. Dr. Lange cuvettes for Ammonium and Nitrite determination. Fig. 16. Closed vials with Kaldnes carriers and buffer solution inside. Fig. 17. Pressure transducer Centrepoint Electronics. Fig. 18. Lab-scale Deammonification reactors with a serial configuration. Fig. 19. Laboratory equipment for measuring physical parameters. Fig. 20. Variations of a)DO, b)pH, c)Conductivity d)Temperature in lab-scale Deammonification reactors during the operational period. Fig. 21. Variations of a)Ammonium, b)Nitrite,Nitrate, c)Alkalinity in lab-scale Deammonification reactors during the operational period. Fig. 22. SAA referred to the biofilm area. Fig. 23. SAA referred to the amount of VSS. Fig. 24. Total nitrogen and Ammonium removal efficiency of lab-scale Deammonification reactors. Fig. 25. Lab-scale Deammonification reactors with a parallel configuration. Fig. 26. Oxygen profiles during intermittent aeration for reactors R1 and R2.

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Fig. 27. Variation of pH of lab-scale Deammonification reactors during the operational period. Fig. 28. Variation of conductivity of lab-scale Deammonification reactors during the operational period. Fig. 29. Variation of temperature of lab-scale Deammonification reactors during the operational period. Fig. 30. Variation of Redox potential of lab-scale Deammonification reactors during the operational period. Fig. 31. Redox profiles during intermittent aeration for reactors R1 and R2. Fig. 32. Variations of Ammonium nitrogen concentration in lab-scale Deammonification reactors during the operational period. Fig. 33. Variations of Nitrite concentration in lab-scale Deammonification reactors during the operational period. Fig. 34. Evolution of Nitrate production in % in lab-scale Deammonification reactors. Fig. 35. Variations of Nitrate concentration in lab-scale Deammonification reactors during the operational period. Fig. 36. Variations of alkalinity in the lab-scale Deammonification reactors during the operational period. Fig. 37. Ammonium concentration and conductivity in the influent in lab-scale Deammonification reactors.

Fig. 38. Correlation between Ammonium concentration and conductivity in the influent in lab-scale Deammonification reactors. Fig. 39. VSS from Kaldnes carriers from lab-scale Deammonification reactors. Fig. 40. SAA referred to the biofilm area. Fig. 41. SAA referred to the amount of VSS. Fig. 42. Comparison between SAA and Deammonification activity in R1. Fig. 43. Comparison between SAA and Deammonification activity in R2. Fig. 44. Comparison between nitrogen removal rate and nitrogen load in the influent. Fig. 45. Total nitrogen removal efficiency of lab-scale Deammonification reactors. Fig. 46. Ammonium removal efficiency of lab-scale Deammonification reactors. Fig. 47. Scheme of the experimental equipment to follow up the batch experiments. xviii

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Fig. 48. a)Ammonium concentration b)Nitrite concentration c)Nitrate concentration d) Mineral N concentration for different aeration ratios and oxygen supply at the end of the batch experiments. Fig. 49. Efficiency of ammonium (a) and nitrogen (b) removal for different aeration rates and oxygen supply. Fig. 50. Ammonium, nitrite and nitrate variation for experiment no 12 (DO=4mg/L and R=1/3). Fig. 51. Partial efficiency in aeration-no aeration periods for DO=4mg/L and R=1/3. Fig. 52. DO profile during batch experiment no 12. Fig. 53. Redox potential variation during batch experiment no 12. Fig. 54. pH and conductivity variation during batch experiment no 12. Fig. 55. Pilot plant Deammonification reactor. Fig. 56. On-line equipment for measuring physical parameters in Pilot plant Deammonification reactor. Fig. 57. DO profile in Deammonification reactor during the operational period. Fig. 58. Variation of pH in operational period.

Deammonification reactor during the

Fig. 69. Variation of conductivity in Deammonification reactor during the operational period. Fig. 60. Temperature profile in Deammonification reactor during the operational period. Fig. 61. Variation of redox potential in Deammonification reactor during the operational period. Fig. 62. Ammonium profile in Deammonification reactor. Fig. 63. Nitrite profile in Deammonification reactor. Fig. 64. Evolution of nitrate production in % in Deammonification reactor. Fig. 65. Nitrate profile in Deammonification reactor. Fig. 66. Alkalinity profile in Deammonification reactor. Fig. 67. COD profile in Deammonification reactor. Fig. 68. COD variations using different pore size filters. Fig. 69. TSS, VSS from biomass of Deammonification reactor. Fig. 70. TSS analyses. Fig. 71. VSS analyses. Fig. 72. SAA referred to the biofilm area. xix

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Fig. 73. SAA referred to the amount of VSS. Fig. 74. Comparison between SAA and Deammonification activity. Fig. 75. Comparison between nitrogen removal rate and nitrogen load in the influent. Fig. 76. Total inorganic nitrogen and ammonium removal efficiency of the pilot plant reactor.

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A CRONYMS AND ABREVIATIONS Anammox AOB BNR BOD CANON COD DO FISH HDPE HRT HSRS Max. Min. M NOB NH3

Anaerobic Ammonium Oxidation Ammonium Oxidize Bacteria Biological Nutrient Removal Biochemical Oxygen Demand Completely Autotrophic Nitrogen Removal over Nitrite Chemical Oxygen Demand Dissolved Oxygen Flourescent In Situ Hybridization High Density Polyethylene Hydraulic Retention Time Hammarby Sjรถstad Research Station Maximum Minimum Mol Nitrite Oxidize Bacteria Free ammonia

NH4+-N NO2--N

Nitrogen in Ammonium form Nitrogen in Nitrite form

NO3--N

Nitrogen in Nitrate form

N2O

Nitrous oxide

NO NO2

Nitric oxide Nitric dioxide

ORP R1 R2 Rpm RBC SAA SBR SHARON

Oxidation Reduction Potential Lab-scale reactor 1 Lab-scale reactor 2 revolutions per minute Rotating Biological Contactor Specific Anammox Activity Sequencing batch reactor Single Reactor for High Activity Ammonium Removal Over Nitrite Standard Deviation Suspended Solids Temperature Total Nitrogen Total Suspended Solids Volatile Suspended Solids Wastewater Treatment Plant

St. Dev. SS T TN TSS VSS WWTP

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A BSTRACT Nowadays there is an increasing need to treat wastewater in a sustainable way and stricter legislation for the quality of effluent is being introduced in many countries. In conventional wastewater treatment plants, nitrogen removal often represents a critical step. A new biological process for ammonium removal from wastewater called Anammox (Anaerobic Ammonium Oxidation) has recently emerged as a promising option for the treatment of wastewater with low C/N ratio. The partial nitritation followed by Anammox process seems to be an excellent alternative for traditional nitrification/denitrification. A six month study was performed at Hammarby Sjรถstad Research Station located in Stockholm. One-stage Deammonification process operation was evaluated in two different system configurations in laboratory scale and in pilot plant. The studies were made to determine the influence of different parameters on the process performance. Analyses of nitrogen forms, alkalinity and COD were also carried out regularly. Lab-scale reactors were run in serial with a subsequent change to a parallel configuration and different strategies of intermittent aeration, what resulted in high efficiency of nitrogen removal from supernatant. Strong relation between conductivity and concentration of inorganic nitrogen in inflow and outflow was observed. In addition, discontinuous laboratory experiments were carried out to find out the best possible strategy of aeration in the partial nitritation followed by Anammox process. DO level and the nitrite production rate seem to be the limiting factors for Anammox reaction in a single reactor. Activity tests based on nitrogen gas production were carried out to determine potential Specific Anammox Activity to compare with nitrogen removal rates in Deammonification process. Bacterial activity at different temperatures has been also analyzed. Key words: Anammox, nitrogen removal, Deammonification, optimization, ammonium, supernatant, partial nitritation/Anammox.

1. I NTRODUCTION 1.1. General background Water is an essential component on earth to keep our lives. Human vital requirements, energy resources and industrial activities depend strongly on the water. Around 70 % of the earth surface is covered by water. 97 % is salty water that constitutes our oceans and seas. Only 3 % of the total volume is fresh water. Around 69 % of this water is part of the glaciers. The rest of the fresh water we find it as ground water and only 0.3 % is surface water found in rivers and lakes. Considering the latest growth of the population, the increasing water consumption and the pollution of the water resources, profitable and effective water treatment technologies become indispensable. Nowadays, there is an increasing necessity of treating wastewater in a sustainable way as well as a strict regulation of the effluents quality. One of the most important problems to achieve a sustainable development in wastewater treatment plants is the high concentration of nitrogen, which is present mainly as ammonium. Moreover, nitrogen removal is the highest investment in wastewater treatment besides sludge treatment. Nitrogen is essential for living organisms; however its discharge into surface water leads to toxicity for aquatic ecosystems, decrease of dissolved oxygen in water and the well known eutrophication process.

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All over the world, an increasing number of water areas are affected by eutrophication. Since the 1800s it has become also a serious problem in the Baltic Sea, which is highly sensitive to the environmental impacts (HELCOM, 2006). The narrowness of the coast that connects the Baltic Sea to the North Sea makes difficult a dynamic water exchange. Furthermore, organisms have to adapt themselves to an environment that is a mixture of fresh and marine water (brackish-water) and this fact makes Baltic ecosystem less resistant to eutrophication (Khalili, 2007). The Baltic Sea, with a water area of 415 000 km2, is an essential water resource for all the people that live around it in Poland, Estonia, Lithuania, Latvia, Germany, Finland, Russia, Denmark and Sweden (Rönnberg et al., 2004). Eutrophication leads to an unbalanced in the composition of the system due to an excessive growth of algae, which decreases visibility in the bottom of the sea and avoids infiltration of sunlight causing the death of the microorganisms. Moreover, a depletion of oxygen level in deep water is caused by decomposition of dead algae. As a result, anaerobic and anoxic ecosystems are created in the water system. Eutrophication increases during summer when water is warmer (Kangro et al., 2007). Nowadays, biological methods are widely used to treat both industrial and municipal wastewater. In most wastewater treatment plants, Nitrogen removal is achieved using the combination of the biological processes of Nitrification/Denitrification. Nitrification process comprises two sequential stages. Firstly, in the Nitritification step, the ammonium is oxidized to nitrite by Nitrosomonas bacteria using aerobic conditions. [1] NH4+ + 1.5O2 → NO2- + 2H+ + H2O In the next Nitratification step, the oxidation of the nitrite to nitrate is carried out by Nitrobacter bacteria. NO2- + 0.5O2 → NO3[2] Denitrification process is the reduction of the nitrate to nitrogen gas under anoxic conditions and with a consumption of a source of organic carbon. This process is carried out by heterotrophic bacteria (Pseudomonas, Paraccocus, Alcalígenes, Thiobacillus, Bacillus). 8NO3- + 5CH3COOH → 8HCO3- + 6H2O + 2CO2 + 4N2

[3]

Differences between Nitrification and Denitrification processes are gathered in table 1.These typical processes succeed with municipal wastewater characterized by a high ratio between organic matter and Nitrogen (C/N). However, operational costs increase considerably when the ratio (C/N) is low. We have examples of nitrogen–rich wastewater effluents like reject water of digested sludge, landfill leachate or effluents from the fish canning industry. Effluents from sludge digestors from agricultural and food factories contain an ammonium concentration up to 2 g NH4+/L (Strous et al.,1997). But these values can be exceeded. For instance, effluents from anaerobic digestion produced in the fish canning factories can have an ammonium concentration up to 5 kg NH4+/m3 (Dapena-Mora et al., 2006). In these cases, the addition of an external carbon source and the high oxygen supply are the main reasons for studying alternative nitrogen re-

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Table 1. Differences between Nitrification and Denitrification processes (Carrillo et al., 2000). Characteristics

Nitrification

Denitrification

Type of microorganism

Autotrophic

Generally Heterotrophic

Grow rate

Days-1

Hours-1

Type of respiration

Aerobic

Anoxic

Changes in pH during the process

Tendency to adification

Tendency to alcalinization

Limiting factors during the process

Low concentration of oxygen Presence of organic matter

Presence of O2 Low concentration of organic matter

moval methods. Using advanced technologies based on biological methods, investment costs of wastewater treatment can be reduced.

1.2. The Anammox process, a short-cut in the traditional nitrogen cycle Nitrogen cycle is one of the most important processes in the Biosphere and represents the different changes between oxidation states of the nitrogen compounds. For a long time, it was assumed that ammonium oxidation could happen only under aerobic conditions, but in 1977, Engelberd Broda predicted the existence of a kind of chemolitoautotrophic bacteria capable of oxidizing ammonium using nitrite as electron acceptor. Recently, Mulder et al. (1995) corroborated this prediction experimentally discovering anaerobic ammonium oxidizers in laboratory. It was Van de Graaf et al. (1995) who evidenced the biological condition of this new process and showed that the nitrite was the electron acceptor and not the nitrate as it was thought in the beginning. Anammox bacteria have been discovered in marine ecosystems, natural environments and wastewater treatment plants. Today, it is known that almost 30-50 % of nitrogen gas produced in N-cycle is due to Anammox bacteria, especially in the marine sediments (Cema, 2009). These novel bacteria have an exceptional characteristic: They consume ammonium for living under anaerobic conditions. With their discovery, a new path in nitrogen removal was formulated and biological processes involving Anammox bacteria became an attractive alternative to the traditional nitrification/denitrification processes. It is extremely difficult to obtain pure cultures of Anammox bacteria because it is hard to isolate them. Nevertheless, several enriched cultures have been established from wastewater and thanks to them it is known some important biochemical and biological aspects of these bacteria. They have an intracellular membrane called anammoxosome (Dalsgaard et al., 2005) where it is believed Anammox process takes place. The oxidation of NH4+ with NO2- is catalyzed by enzymes in this compartment with hydrazine and hydroxylamine as intermediates. The anammoxosome constitutes more than the 30 % of the cell volume (Jetten et al., 2005). The Anammox bacteria discovered up-to-date (Table 2) belong to the order of the Planctomycetales and there are three different genus: Brocadia, Kuenenia and Scalindua. Brocadia and Kuenenia were found in wastewater treatment systems. The genus of Scalindua has also been discovered in the seawater.

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Table 2. Types of Anammox bacteria (Zhang et al., 2007). Genus

Species

Source

Brocadia

Candidatus Brocadia anammoxidans Candidatus Brocadia fulgida

Wastewater Wastewater

Kuenenia

Candidatus Kuenenia stuttgartiensis

Wastewater

Scalindua

Candidatus Scalindua brodae Candidatus Scalindua wagneri Candidatus Scalindua sorokinii

Wastewater Wastewater Seawater

Others

Candidatus Jettenia asiatica Candidatus Anammoxglobus propionicus

Not reported Synthetic water

The Anammox process, which means ANaerobic AMMonium OXidation, represents a new path in the nitrogen cycle (Fig. 1). Basically, Ammonium is converted under anaerobic conditions to Nitrogen gas using nitrite as an electron acceptor. The global reaction, including cell synthesis, is as follows: NH4+ + 1.32 NO2- + 0.066 CO2 + 0.066 H+ → 0.066 CH2O0.5N0.15 (Anammox bacteria) + 1.02 N2 +0.26 NO3- + 1.96 H2O [4] As we can see according to the reaction stoichiometry, the principal product is Nitrogen gas. However a small fraction of nitrite is oxidized to nitrate. Nitrite concentration should exceed ammonium concentration, with a ratio between nitrite and ammonium (NO2--N/NH4--N) present in wastewater equal to 1.32. The process is autotrophic, Anammox culture use CO2 as the unique source of carbon. Hydrazine and hydroxylamine are the intermediates in the process. Anammox bacteria are characterized by slow growth rate (0.003 h-1) with a doubling time of 10 days (Jetten et al., 2001) and low biomass yield. This means that a low amount of sludge is produced but efficient sludge retention is required (Strous et al., 1997a). The reaction is inhibited by molecular oxygen (Jetten et al., 2001) and irreversible inhibited by nitrite when NO2--N exceed a concentration of 70 mg NO2--N/L for several days (Dongen et al., 2001).

Fig. 1. Short-cut in nitrogen cycle using Anammox process (www.paques.nl).

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Evaluation of Deammonification process performance for supernatant treatment

It has been reported by Güven et al. (2005), that Anammox process is irreversible and completely inhibited by even lower concentrations of alcohols like methanol (1mM), which is commonly added to adjust the pH in the partial nitrification step. Mechanical stress was also identified as an inhibitory factor (Arrojo et al., 2006). The growing of these microorganisms can be described using following a Monod equation, which shows the dependence with the limiting substrate (Fernández et al., 2007).

µ = µmax ⋅

S − Kd KS + S

[5]

Where: µ - growing rate, d -1

µmax - maximum growing rate, d -1 S - concentration of substrate, g L-1 K S - Affinity constant, g L-1 K d - decay coefficient, g g-1 d-1 We can rewrite the general equation considering the ammonium as the limiting substrate:

 NH 4 +  µ = µmax ⋅ K S +  NH 4 + 

[6]

If the nitrite is the limiting substrate, the equation should be written as:

 NO2 −  µ = µmax ⋅ K S +  NO2 − 

[7]

Fluorence In Situ Hibridation (FISH) has been used to detect specific species of Anammox bacteria. Its characteristic reddish color (Fig. 2) is probably due to Cytochrome C, one of the proteins present in bacteria cells (Dosta et al., 2008).

Fig. 2. Granules of Anammox bacteria.

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TRITA LWR Degree Project

Anammox process has been widely investigated in Europe (mainly in Netherlands and Germany) and this leads to a big amount of publications in this area. Talking about Sweden, the most important group of researchers is in Stockholm at the Royal Institute of Technology (Department of Land and Water Resources Engineering). Advantages of the Anammox process The Anammox process is especially suitable for wastewater streams with high nitrogen load and deficiency of carbon source. In these cases, Anammox process has become an interesting alternative for the nitrogen removal with important advantages like: • High efficiency of nitrogen removal. • No need of external organic matter addition because it is an autotrophic process. • Reduction of 60 % of energy supply for aeration. • Minimize the environmental impact reducing 95% CO2 emissions to the atmosphere because the Anammox process consumes CO2. • Decrease excess sludge generation. • Save operational costs up to 90 % compared with the traditional processes (Jetten et al., 2001). • No need of chemicals addition. • Up to 50% less of space requirements. Nevertheless, full-scale application of this process is limited by the slow growth rate of the microorganism (0.072 d-1 measured at 32° C) (Trigo et al., 2006) and a long start-up initial period. Start-up periods from 2 months to 3.5 years were described by Szatkowska et al. (2007). Nowadays, the Anammox process is widely applied mainly in two types of processes: Treatment of landfill leachate or reject water from digested sludge (normally called supernatant). The reason is that Anammox process is especially adequate for such streams with high level of ammonium. The main difference between these two types of streams is the concentration of organic matter, expressed as the COD value. Anyway, a characteristic of both media is a low biodegradable COD/N ratio. But Anammox process can find another areas of application as digested fish canning effluents (Dapena-Mora et al., 2006), tannery wastewater (Paques, 2007), piggery manure (Ahn et al., 2004) or slaughterhouse wastewater (Siegrist et al., 1996) and whatever other industry which produces wastewater with high inorganic nitrogen concentration.

1.3. New biological processes for nitrogen removal from wastewater New technologies are being developed for nitrogen removal, some of them based on the Anammox reaction. Parallel research carried out by different research groups in some countries makes difficult to find clear terminology in literature. To treat wastewater using Anammox bacteria, it is required to provide nitrite as electron acceptor. Nitrite can be produced applying many reactor configurations and under different operation conditions. 1.3.1. CANON process The CANON process, which means Completely Autotrophic Nitrogen Removal Over Nitrite, consists of the removal of ammonium from wastewater in an oxygen-limited, single reactor. In this process the

6

Evaluation of Deammonification process performance for supernatant treatment

ammonium oxidation to nitrite and the Anammox reaction are combined in the same reaction (Gut, 2006): NH3 + 0.85 O2 → 0.11NO3- + 0.44N2 + 0.14H+ + 1.43 H2O [8] 1.3.2. Oland process Oland process, Oxygen–Limited Nitrification and Denitrification, is a new process for ammonium removal in one step without presence of organic carbon (Dapena Mora, 2008). NH4+ + 0.75O2 → 0.5N2 +1.5H2O + H+ [9] 1.3.3. SHARON process The SHARON process, Single reactor for High activity Ammonia Removal Over Nitrite, is performed in a completely mixed, single reactor. It consists of the oxidation of ammonium to nitrite, only the nitritation step keeping the oxygen concentration in a low level (Szatkowska, 2007). NH4+ + 0.75O2+ HCO3- → 0.5 NH4+ + 0.5NO2- + CO2+ 1.5 H2O [10] The main advantage is the reduction in oxygen supply (Hellinga et al., 1998). 1.3.4. Deammonification process Deammonification process converts part of the ammonium present in wastewater to nitrate and part to nitrogen gas (Siegrist et al., 1998). It is based on the CANON process with performance of nitritation and Anammox process together under limited oxygen conditions. This process is explained deeply in chapter 2.

1.4. Swedish wastewater treatment development Stockholm is the capital of Sweden with a population of 800 000 inhabitants corresponingd to 8 % of the Swedish population. It is divided and surrounded by water: situated between Mälaren Lake, Swedish’s third largest lake, and the Baltic Sea. It is built on 14 islands on the south east of Sweden and more than the 30 % of the city area is formed of waterways. In Sweden, water is considered indispensable but also wastewater has been treated as a resource to a certain extent with some important applications like the use of the sludge in agriculture for nutrient supply in the soils, source of energy (biogas), and recuperation of sand or heating source. Wastewater Treatment Plants (WWTP) in Sweden have experimented a gradually development in time since they started in the 1930’s with a simple mechanical treatment. Later, during the 1950’s they incorporated biological processes for treating organic materials. In 1970’s chemical precipitation for Phosphorus removal was introduced and during the 1990’s Nitrogen removal as well. In order to increase the efficiency, during the period between 1930-1990 new treatments were incorporated into the old ones to satisfy increasingly strict effluent standards (Hultman et al., 2009). Nowadays, the main objectives in wastewater treatment are: Minimize environmental impact considering green house gases, energy savings, reuse Phosphorus in agriculture, increase pharmaceuticals and antibiotic removal and improve Nitrogen removal processes. Concerning to WWTP infrastructures, Henriksdal is the biggest WWTP in Stockholm and one of the largest in Europe. It is an underground plant with a surface of 300 000 m2 and it is formed by 18 kilometers of subterranean tunnels. It was opened in 1941 and its capacity was

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TRITA LWR Degree Project

Fig. 3. WWTP’s in Stockholm. extended in 1953 to include biological and chemical treatments. Nowadays, it receives 355 000 m3 of wastewater each day from one million people in Stockholm and other local councils like Huddinge, Haninge, Nacka and Tyresö. At Henriksdal, wastewater is treated with chemical, mechanical and biological processes. Nowadays Stockholm city and its surroundings have another important WWTP like Bromma, Himmerfjärden, Käppala and Loudden (Fig 3). • Bromma is the second biggest WWTP that serves the north–western parts of Stockholm. It has been designed to treat a sewage flow of 160 000 m3 each day. • Himmerfjärden treatment plant is situated in the south of Stockholm by the shore of Himmerfjärden bay and it serves a total of 250 000 persons and several industries. It was constructed between 1970 and 1973 and it has capacity to receive 130 000 m3 of wastewater per day. It is a conventional WWTP that combines mechanical, chemical and biological treatment (Fig. 4). Nowadays, Himmerfjärden coastal is a sensitive area affected by the Eutrophication problem (Szatkowska, 2007).

Fig. 4. Himmerfjärden WWTP-pilot plant for studies of Anammox process. 8

Evaluation of Deammonification process performance for supernatant treatment

• Loudden is another underground treatment plant operating since 1950 with capacity to treat sewage of 50 000 people. It incorporated biological treatment in 1960. • Käppala WWTP is also an underground plant designed for receiving 220 000 m3 of wastewater each day. The treatment consists on mechanical, chemical and biological processes with a final filtration step. Since 1989, the treated water is not discharged into Lake Malarën anymore but into Saltsjön Lake in the sea area.

2. C HARACTERIZATION OF D EAMMONIFICATION PROCESS 2.1. General description In the 1990s, a novel process was proposed to treat effluents with a high load of nitrogen. Deammonification process, also called partial nitritation/Anammox process represents a short pathway in the N-metabolism and consists on 2 steps process: • Partial Nitritation where part of ammonium (50-60 %) is oxidized to nitrite: NH4+ + 1.5 O2 → NO2- + H2O + 2 H+

[11]

• Anammox reaction. Bacteria use ammonium and nitrite as substrates to produce nitrogen gas. This step implies simultaneous removal of nitrite and ammonium: NH4+ + NO2- → N2 + 2 H2O

[12]

This new process has important advantages compared to conventional nitrification/denitrification such as lower aeration costs and no addition of external carbon source which means a reduction in operational costs of 30%. Deammonification process can be applied by using two separate reactors with a partial nitrification stage and the Anammox stage or only one reactor keeping microaerobic conditions. Both processes are carried out by different microorganisms: in the first step, the ammonium is partially oxidized by aerobic autotrophic ammonia oxidizers (AOBs) and in the second stage the remaining ammonium is oxidized to nitrogen gas by anaerobic autotrophic ammonia oxidizers (Anammox). Comparing the two steps in the Deammonification process, it is shown that anaerobic ammonium oxidation is more favorable energetically than the traditional aerobic oxidation (Table 3). Table 4 shows the main factors that influence the Deammonification process.

Table 3. Parameters of Ammonium oxidation in aerobic and anaerobic conditions (Jetten et al., 2001). Parameter

Nitrification NH4+ + O2 → NO2-

Anammox NH4+ + NO2- → N2

Unit

Free energy

-275

-357

KJ/mol

Biomass yield

0.08

0.07

Grow rate

0.04

0.003

1/h

Doubling time

0.73

10.6

days

mol/mol C

Ks NH4+

5-2600

5

µM

Ks NO2-

N/A

<5

µM

10-50

N/A

µM

Ks O2

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Table 4. Main factors influencing Deammonification process. Deammonification process Partial nitritation

Anammox process

Oxygen supply

Oxygen-limited supply

Supernatant composition

Nitrogen load in the inflow

Ratio nitrite/ammonium in the outflow

Ratio nitrite/ammonium in the inflow

Hydraulic Retention Time (HRT)

Hydraulic Retention Time

pH decrease

pH increase

Consumption of alkalinity

Nitrite concentration inside the reactor

Free nitrous acid and free ammonia concentrations

SAA of bacterial culture

Temperature

Temperature

Applications of Deammonification process Full-scale applications with different designs and operation models exist at Rotterdam (Holland), Hattingen (Germany), Strass (Austria) and Himmerfjärdsverket (Sweden). Deammonification process can be applied to effluents with a high concentration of ammonium. Some typical applications are: Reject water from digested sludge in municipal wastewater treatment Leachate from composting and landfills Food industry Manure processing industry Fertilizer industry Petrochemical industry Metallurgical industry Yeast industry Mining industry Alcohol production industry Starch processing industry

2.2. Operational parameters Knowledge about operational parameters that influence wastewater treatment performance is necessary to implement the process with minimal costs and maximum efficiency. The main factors that have an effect in the activity of bacteria are described briefly below. 2.2.1. Dissolved Oxygen Dissolved oxygen (DO) is the amount of oxygen that is dissolved in the sludge inside the reactor, and it is measured in mg/L. The dissolved oxygen is a very important parameter in the Deammonification process because in the first step of the process, partial nitrification, oxygen is demanded. Bacteria need it to oxidize ammonium to nitrite. However, the second part of the process is inhibited by oxygen. Without aeration, the amount of oxygen in the sludge comes from the oxygen in the air, but this quantity is not enough to carry out the first step in the Deammonification process, and it makes necessary an external supply of oxygen in the reactor. Unsuitable or overage of oxygen can inhibit either nitrification or Anammox process, respectively. A certain level of DO must be reached

10

Evaluation of Deammonification process performance for supernatant treatment

to provide sufficient oxygen for a complete nitrification. The dissolved oxygen concentration has a significant effect on the growth and activity of nitrifying bacteria, even in some cases can be the limiting substrate. The United States Environmental Protection Agency (U.S. EPA, 1993), recommends DO values over 2.0 mg/L for nitrification. However full nitrification has been reported in systems with DO values lower than 2.0 mg/L. Even successful nitrogen removal has been reached in systems with a value of DO of less than 1mg/L (Holman & Wareham, 2003). Strous et al. (1997b) showed that Anammox process was inhibited reversibly by oxygen. Nevertheless, it is possible a stable coexistence of Anammox and nitrifying bacteria under microaerobic conditions despite of decreasing the maximum Anammox activity. This coexistence is possible due to the oxygen gradients on the biofilm: Nitrifiers grow in the outside part of the biofilm (aerobic conditions) while Anammox develop inside in an anaerobic environment. A high DO concentration will cause an excessive growth of nitrifying bacteria in the reactor. Furthermore, this high concentration of oxygen produces oxygen diffusion deeper in the biofilm, which causes less or no anaerobic conditions for Anammox bacteria. However, low DO concentration will lead AOB to be inactive and less nitrite produced. Taking into account the different oxygen requirements of both microorganisms, intermittent aeration supply in the reactor can be a good choice for using in wastewater treatment because it reduces aeration costs compared to continuous aeration, while nitrogen is removed by Anammox bacteria in the anoxic period. Third et al. (2005) reported that Anammox was not inhibited using intermittent aeration (20 minutes aeration and 30 minutes without aeration) in a CANON reactor with high ammonium removal. Temperature and mixing of the liquid of reaction are the main factors that affect oxygen level inside the reactor. Thereby, cold water can hold more oxygen than warm water. 2.2.2. pH pH is a measure of acidity or alkalinity of a solution, and it indicates the concentration of the hydronium ion [H3O+] present. Pure water at 25 째C has a neutral pH, equal to 7. pH is responsible for nitrous acid concentration and ammonia concentration. Low pH values cause high nitrous acid concentration whereas high pH values lead to high ammonia concentration, what inhibits Deammonification process. In biological treatment, the pH gives information about the biological reactions that take place in an aerobic/anoxic process, for instance, increase in pH for ammonification and denitrification, and decrease in this value due to nitrification (Tanwar et al., 2008). The control of the pH in the Deammonification process is essential because there is a narrow range in which both nitrifying and Anammox bacteria coexist properly. The optimum pH range for the activity of Nitrosomonas is between 7.2 and 8, and a physiological pH interval for Anammox bacteria between 6.7 and 8.3 was determined by Strous et al, (2000) with an optimal value for operation of 8. Egli et al. (2001) carried out batch test to study the effects of pH on Anammox activity and there was not observed Anammox activity at pH 6 and 6.5.

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2.2.3. Conductivity The conductivity is a measure of the water’s ability to allow the electric current through it, and it is measured in S/m. Conductivity varies with temperature, increasing proportionally with it. The concentrations of NH4+ and HCO3- ions in the supernatant contribute to the total value of conductivity. These two ions have opposite but the same absolute value of charge, and for this reason changes in the conductivity values are observed during different biological nitrogen removal processes. This means that these processes can be followed by very easy with simple conductivity measurements (Szatkowska, 2004). Since Deammonification process produces nitrogen gas, the ions decrease during the reaction period, and also the conductivity. So this parameter is a useful indicator of the reaction progress. Use of conductivity to monitor the Deammonification process Offline measurements of nitrogen forms to control the performance of the process are time consuming and costly, and the time lapse may change properties in the sample to be analyzed. But if the dynamic behavior of nutrient concentration in the reactor system with treatment is related with monitored physical parameters, the process may be better controlled, and profitable (Tanwar et al., 2008). Conductivity can be used to monitor biological processes because it can be measured in an easy way. It gives information about chemical composition of water and it is directly related to the amount of ions in the wastewater and their mobility. Conductivity changes because of transformations from ammonium and hydrogen carbonate ions into molecules and its relation with different nitrogen forms. The conductivity parameter provides information concerning the presence of inorganic dissolved solids such as nitrate, sulfate, phosphates, magnesium, iron... Non-ionic organic compounds do not conduct electrical current very well so their value of conductivity in water is low (Szatkowska, 2007). 2.2.4. Temperature Temperature is another important parameter in the Deammonification process. The optimal temperature range for growing of Nitrosomonas bacteria, responsible for the nitration process, is 25-30 °C, but operation of treatment plants rarely occur at temperatures above 25 °C, for economic reasons. Below 5 °C nitrifying bacteria activity is suppressed. Some authors found out that the optimal temperature for Anammox bacteria was around 30-40 °C. Although it was proved by Cema et al. (2007) that Anammox process could be carried out at temperatures around 20 °C in a rotating biological contactor (RBC). Dosta et al., (2008) found that the maximum activity for non-adapted Anammox bacteria was observed in the range 35-40 °C, whereas that a temperature of 45 °C produced an irreversible decrease of the Anammox activity. Moreover, it was observed the adaptation of the biomass to temperatures about 15 °C in a sequential batch reactor (SBR), despite the performance of the reactor decreased and the system became unstable because of the nitrite accumulation. Strous (2000) observed that the optimal temperature for Anammox bacteria is 40±3 °C. Between 20 and 37 °C the Anammox activity dependence with temperature follows Arrhenius law. At a temperature of 10 °C or less, no Anammox activity was found.

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Evaluation of Deammonification process performance for supernatant treatment

Additionally, Egli et al. (2001) demonstrated that the Anammox bacteria found in a WWTP are active at temperatures within the range of 6-43 °C and an optimum at 37 °C. For the optimal temperature, the pH range is between 6.5 and 8.5. It is generally known that an increase in temperature increases the rate of chemical and biological reactions. The main limitations of high temperatures are the expensive heating costs and the possible harm for bacteria. 2.2.5. Oxidation Reduction Potential (ORP) Oxidation Reduction Potential or Redox Potential is a measure of the tendency of chemical species to gain or to lose electrons and thereby be reduced or oxidized respectively. This parameter has been used in wastewater treatment as an indicator of microbial activity since 1936, and it is measured in volts (V) or milivolts (mV). The displayed voltage shows the ability of water to oxidize contaminants in it, with no correction for solution temperature. The higher the potential is, the greater the affinity of the species for electrons and tendency to be reduced. The Redox potential is a measure of the activity of electrons, not a measurement of concentration directly. It is related to pH and oxygen content. It is analogous to pH since pH measures the activity of protons. ORP’s most common application in wastewater treatment is the Biological Nutrient Removal (BNR). This application requires multitude of environment conditions like aerobic, anoxic and anaerobic for efficient removal of nutrients. During anaerobic and anoxic conditions the dissolved oxygen tends to go to zero, therefore ORP can be used as a better indicator of the activity of the microorganisms (Buddhavarapu & Inniss, 2006). Fig.5 shows ORP intervals for different wastewater processes. ORP values below -200 mV are indicative of anaerobic or reducing conditions. ORP values in the range -200 and +200 mV are for anoxic conditions. Aerobic or oxidative conditions are represented by values above +200 mV. Activated sludge process occurs under aerobic conditions, methanogenesis takes place in anaerobic conditions and nitrification and denitrification require anoxic and aerobic conditions respectively.

Fig. 5. Redox potential ranges (mV) for typical wastewater processes (Buddhavarapu & Inniss, 2006).

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In biological treatment, a change of pH and ORP usually reflects biological reactions in an aerobic/anoxic process. The ORP depends on temperature and also is connected with DO concentration, organic substrate, activity of microorganisms and toxic compounds in a reactor, so many substances in a process can change ORP value. This parameter also indicates some operational conditions as under- and overloading and underand overaeration (Hao & Kim, 2000). It has been reported by Holman & Wareham (2003), Tanwar et al. (2008), Ridenoure (2004) that the same processes can take place at different absolute values of ORP but show the same tendency in ORP change. One example of a full-scale plant where the biological nitrogen removal system is monitored and controlled using changes but not direct values of ORP measurements is Käppala, in Sweden. Implementation of the Redox Potential as a controlling parameter has improved the removal efficiency in more than 5% (Käppalaförbundet, 2007). ORP profiles can be drawn taking in account ORP values during the process operation. Figure 6, presented by Ridenoure (2004), explains the change of ORP in the nitrification/denitrification process. When the aeration begins, ORP increases rapidly because of increasing DO concentration. The oxygen increases ORP because of the increasing oxidizing ability of the solution. When the conversion from ammonium to nitrate stops, the oxygen uptake rate of nitrifiers decreases, which leads to higher DO levels and ORP accordingly, because of increased electron acceptors. This point is called “Ammonia elbow”, and it can mean that all NH4-N has been oxidized to nitrate or insufficient alkalinity. Also during aeration, the COD elbow occurs before NH4-N utilization ends and it is usually viewed as a smaller bump than ammonia, indicating that COD is depleted. With the start of anoxic phase ORP decreases rapidly because DO level also decreases. When denitrification process ends, ORP begin to decrease even faster and the “Nitrate knee” is observed.

Fig. 6. Exaggerated ORP profile for an intermittent aeration wastewater treatment system (Ridenoure, 2004).

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Evaluation of Deammonification process performance for supernatant treatment

3. A IMS OF THE T HES IS The aim of this thesis was to apply the Anammox process for nitrogen removal from ammonium-rich supernatant. The main goal of these studies was to study the partial nitritation/ Anammox process and optimize the system performance, specially focused on implementation of intermittent aeration. The process was evaluated in lab-scale with different configurations and in pilot plant. The specific objectives of this thesis were: • Literature review about nitrogen removal from wastewater. • Detailed study and better understanding of Deammonification process performance for supernatant treatment. • Operate the Deammonification process in order to obtain optimal conditions for bacteria growth. • Examine operational parameters that affect Deammonification process performance. • Evaluate the use of physical parameters as a tool to monitor and control the process. • Find correlations between physical parameters and the reactor performance. • Monitor and control of one-stage Deammonification process in labscale. • Perform SAA tests to compare potential nitrogen removal rate with the Deammonification process activity, and check the temperature influence on Anammox reaction. • Determine the weight of biomass developed on Kaldnes carriers. • Estimate the ammonium and total nitrogen removal efficiency of the process in different configurations. • Optimize the process by changing operational parameters to get high removal rates. • Determine the best aeration strategy and level of dissolved oxygen for Deammonification process using batch experiments. • Up-scale Deammonification process in pilot plant. • Evaluate the influence of the nitrogen load in the process performance. • Obtain practical skills in laboratory work: calibration of equipment, measuring physical parameters, doing chemical analysis, maintaining and cleaning reactors, pumps and pipes…

4. E XPERIMENTAL S TRATEGY AND METHODOLOGY 4.1. Hammarby Sjöstad Research Station (HSRS) Hammarby Sjöstad Research Station is a research center to evaluate new technologies and systems for wastewater treatment in pilot scale (Fig 7). It was built in 2003 and it is situated on top of Henriksdals WWTP in Stockholm. It belongs to IVL and the Royal Institute of Technology (KTH). It was designed to treat wastewater from around 600 people in Hammarby Sjöstad. It consists of four treatment lines for chemical, biological and physical treatment of wastewater. Three of them have a capacity of 1-2 m3/h and the other is a low capacity line.

15

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TRITA LWR Degree Project

Fig. 7. Facilities at HSRS (www.sjostadsverket.se). The main objectives are to reduce by 50 % the amount of heavy metals and non biodegradable harmful chemicals and hazardous substances present in wastewater, reuse 95% of the phosphorous in agriculture and decrease nitrogen content up to 6 mg/l and phosphorous concentration up to 0.15 % in the treated wastewater. The plant was also designed for testing and optimization of new technologies and processes.

4.2. Studies on Deammonification process All the experimental studies have been performed at HSRS during six months, from October (2009) to March (2010). The research can be divided into two general experimental parts (Fig. 8 and 9): • Experiments in laboratory scale: From October 2009 to December 2010. • Experiments in pilot plant: From January 2010 to March 2010.

Fig. 8. Main events during the experimental work at HSRS.

16

Evaluation of Deammonification process performance for supernatant treatment

Fig. 9. Localization of laboratory and Pilot plant at HSRS.

4.3. Supernatant Characteristics The influent for all the Deammonification studies performed at HSRS was supernatant after dewatering digested sludge. Anaerobic sludge digestion is a typical process to reduce sludge volume and bad odor and produce biogas. Normally, during the anaerobic digestion of the sludge, around a 50% of nitrogen is discharged as ammonium while organic carbon is transformed into methane (Siegrist, 1996). After the digestion, the sludge is dewatered to separate a solid phase, which can be used in agriculture. The reject stream (supernatant) is characterized by high ammonium concentration (200-700 g m-3) (Cema, 2009) and little amount of biodegradable organic matter. It was reported that the ammonium load in the supernatant is up to 15-20 % of the total nitrogen load in the influent wastewater (Siegrist, 1996). Handling of produced supernatant usually means a problem in wastewater treatment plants. Conventional treatment for supernatant is a traditional nitrification/denitrification process returning the reject water to the head of the treatment plant. The main problem is that the nitrogen load in the inflow due to supernatant recirculation increases in 15-20 % and also aeration costs (Gut, 2006). For this reason separate treatment becomes necessary to decrease nitrogen load. Many researchers have proposed that partial nitrification/Anammox process could be a better alternative with less oxygen and carbon source requirements and high nitrogen removal efficiency. At the beginning of the experimental work different supernatants were analyzed to find which one had the most suitable characteristics to be used in the experimental work: • Supernatant from Hammarby Sjöstadsverk • Supernatant from Himmerfjärden • Supernatant from Bromma The ammonium concentration was different depending on the source but even for the same source, it changed in weeks or even days. Supernatant composition is influenced by operational problems and the inflow at the WWTP. Analyses were repeated during the experimental studies to notice the probability of a changeable influent composition.

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TRITA LWR Degree Project

Fig. 10. Compacted Kaldnes carriers with biomass attached. The concentration of the other nitrogen forms (NO2--N and NO3--N) was quite low. The pH value was around 8 and the Chemical Oxygen Demand (COD) normally lower than 1000 mg O2/L. The alkalinity value can be not high enough to allow nitrification and, in this case, an additional alkalinity source has to be added (Jeavons et al., 1998). One advantage was the high temperature of the supernatants (around 20 °C). Phosphorus concentration can be important (0.6-48.6 mg Ptot/L) but this thesis was only focused on nitrogen removal.

4.4. Kaldness biofilm carriers Kaldnes carriers are small plastic cylindrical biomass rings made of highdensity polyethylene (HDPE) with a cross inside and fins on the outside.(Fig 10) Their diameter is 10 mm and they have a length of 7 mm. Their density is 0.96 kg/l, which allows them to be suspended in the water (Lekang, 2000). Kaldnes carriers are designed to make the biomass grow in the inner area of the carriers (effective specific surface area) while the outer surface is cleaned from the biomass attachment by frictions between carriers. Their effective specific surface area equals to 500 m2/m3 when they are completely packed. Biofilm carriers have been used in wastewater treatment for the coexistence of both nitrifying and Anammox bacteria in one single reactor. The biomass attached to Kaldnes carriers in the Deammonification process form a two-layer structure, which has nitrifying bacteria in the outer layer with aerobic conditions and Anammox bacteria are located in the inner part, under an anoxic environment. The mechanism of the Partial nitritation/Anammox process in the biofilm is shown in the figure 11. Because of the extremely low growth rate of Anammox culture, this kind of biomass carriers is widely use to guarantee almost total biomass retention inside the reactors, particularly during the start-up (Dapena-Mora, 2004).

18

Evaluation of Deammonification process performance for supernatant treatment

Fig. 11. Scheme of the chemical reactions occurring within the biofilm (Cema, 2009). Besides being employed in nutrient removal processes, Kaldnes carriers have some other applications such that phosphorous removal, odourcontrol, thermophilic processes or solid waste (www.anoxkaldnes.com) (Fog 12).. Biomass measurements In order to determine the amount of biomass developed on the rings, the procedure is the following (Standard Methods, 1999): 1. Use a needle and destilled water to remove the biomass from a fixed number of Kaldnes carriers. In our case, 4 rings were used. 2. Filter the obtained suspension using a 1.6 ¾m pore size filter. 3. Remove the filter from the base of the funnel used to do the filtration and put it in an Aluminum dish. Previously, it was checked the capacity of Aluminum for not changing its weight at high temperatures. 4. Dry at least one hour at 103-105 °C in an oven and weigh it in an analytical balance to determine the Total Suspended Solids (TSS). 5. Place the filter and the dish in a muffle furnace for ignition at 55 °C during 40 minutes and finally weigh it to determine Volatile Suspended Solids (VSS).

Fig. 12. Kaldnes carriers with biomass attached for industrial applications (www.anoxkaldnes.com). 19

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

Fig. 13. Filter and Aluminum dish after ignition. Total Suspended Solids (TSS) can be calculated as follows:

 = ( A − B ) TSS  g ring   R

[13]

Where: A - weight of residue + filter and Aluminum dish after the oven (g) B - weight of filter and Aluminum dish (g) R - number of used rings TSS are the amount of inorganic and organic matter present in wastewater. Volatile Suspended Solids (VSS) can be calculated as follows:

 = ( A − D ) VSS  g ring   R

[14]

Where: A - weight of residue + filter and Aluminum dish after the oven (g) D - weight of residue + filter and Aluminum dish after ignition (g) R - number of used rings VSS represent the quantity of biomass attached to each ring: nitrifying, Anammox and also denitrifying bacteria (Fig 13). A progressive rise of these values means that the amount of bacteria has increased, and it is reflected in an increment of the biofilm thickness. Additionally, the ash content can be calculated in the following way:

% Ash =

TSS − VSS (D − B ) = ⋅ 100 (A − B) TSS

[15] The ash content can be associated with the amount of inorganic matter present in the sample.

20

Evaluation of Deammonification process performance for supernatant treatment

Taking in account that 57 rings occupied a volume of 60 ml, it was possible to express the amount of TSS and VSS in g/L.

4.5. Measurements and Analyses 4.5.1. Physical parameters The following physical parameters were monitored everyday in the different systems studied during the research period: • Dissolved Oxygen • pH • Conductivity • Temperature • Redox Potential The measurement of physical parameters can be done off-line or on-line. On-line equipment provides a more efficient control of the process, with more reliable and accurate values than the manual measurements (Ridenoure, 2004). Additionally, it was reported by Holman (2003) that implementation of on-line control for a nutrient removal system can provide up to 30 % energy savings if it is compared to strict timer-based operation. 4.5.2. Chemical Analyses Besides physical parameters, chemical analyses in influent and effluent were carried out regularly to follow up and monitor the process progress. Analyses of nitrogen in different forms (Ammonium, Nitrite, Nitrate, Total Nitrogen), have been performed according to the hydraulic retention time (HRT) in the reactor. Moreover, Alkalinity (or Acid Capacity) and COD were measured to increase the knowledge about the process progress. Alkalinity or Acid capacity is a measure in mg/L of the buffering capacity of water and wastewater, and it is equal to the stoichiometric sum of the bases in solution, and can be expressed by the formula: A= [OH-] + [HCO3-] + 2[CO3-2]-[H+]

[16]

In natural water, carbonate alkalinity constitutes most of the total alkalinity caused, mainly, by decomposition of carbonate rocks. Alkalinity

Fig. 14. Relation between pH and alkalinity forms (Szatkowska, 2007).

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TRITA LWR Degree Project

is strongly depended on pH value. Figure 14 shows the dependence between the pH and the alkalinity forms. COD test is used to determine in an indirect way the amount of organic compounds in water, and measure its quality. The higher the COD is, greater the amount of organic material. For these analyses, a spectrophotometric method was applied, using Dr. Lange cuvettes and a Dr. Lange Xion 500 spectrophotometer (Fig. 15). Samples were taken from both inflow and outflow and they were filtrated with a 1.6 µm pore size prefilter and a 0.45 µm pore size filter. Sometimes, due to not having cuvettes in the required measurement range because the concentration expected was too high, it was necessary to dilute the samples with distilled water. After analyzing, the samples were kept in the freezer. The analyses were made following the detailed working procedure supplied in each package. The list of standard cuvettes produced by the company Hach Lange GMBH used for analyses is shown below: • NH4-N LCK 303, 2-47 mg/L • NH4-N LCK 302, 47-130 mg/L • NO2-N LCK 342, 0.6-6 mg/L • NO3-N LCK 340, 5-35 mg/L • Acid Capacity Ks 4.3 LCK 362, 0.5-8.0 mmol/L • COD LCK 314, 15-150 mg/L O2 • COD LCK 514, 100-2000 mg/L O2 4.5.3. Specific Anammox Activity (SAA) tests to determine Nitrogen gas produc-

tion Anammox bacteria use ammonium and nitrite as substrate to produce nitrogen gas. Dapena-Mora et al. (2004) have reported that batch Anammox activity measurements are useful in order to monitor the

Fig. 15. Dr. Lange cuvettes for Ammonium and Nitrite determination.

22

Evaluation of Deammonification process performance for supernatant treatment

operation of the process and to assess its long term performance. For this reason, batch tests to determine SAA were done according to Dapena-Mora et al. (2007). Batch tests are based on measuring the overpressure generated by the nitrogen gas produced in closed vials (Fig 16). The measurement of the amount of nitrogen gas can be in terms of VSS as it is usually used with granular biomass (Dapena-Mora et al., 2007) but it is more useful for systems with biomass attached to refer it to the biofilm area. The methodology used for determination of SAA was adapted from the works of Dapena-Mora to biofilm systems (Malovanyy, 2009). In each test, some pressurized Pyrex vials with a total volume of 38 mL and a fixed number of 15 Kaldnes rings with attached bacteria were employed. The vials were closed with a cap with rubber septum capable to stand about 2 bars of pressure, to prevent the escape of gas. The cap had a hole on the top so the way to access inside the bottle was with a needle through the septum. The rings were washed three times with phosphate buffer (0.14 g/L KH2PO4 and 0.75 g/L K2HPO4) with a pH of 7.8 manually prepared, and were put inside the vials with the same buffer until a volume of 24 mL was reached. The vials were closed and a needle connected to nitrogen gas line was inserted through the septum. N2 gas was inoculated for a few minutes to remove all the oxygen inside the vials while another needle was inserted to be the outlet, to remove the gas excess from the vials. Then they were put in a thermostatic water bath for 10-15 minutes until the desired stable temperature were reached. Then the substrates (0.5 mL of NH4Cl and 0.5 mL of NaNO2 to fix initial concentrations of ammonium and nitrite inside the vials in 70 mg N/L) were added with a syringe. The pressure was equalized to the atmospheric one with another needle and in that moment the time was set to zero when the initial pressure was measured. The vials remained inside the water bath all the time that the test lasted (2 or 3 hours depending on the temperature of operation). By measuring the overpressure in the headspace every 30-40 min with a pressure transducer (Fig 17) produced by Centrepoint Electronics which measures overpressure in a range from 0 to 15 psi, the production of nitrogen gas can be determined.

Fig. 16. Closed vials with Kaldnes carriers and buffer solution inside. 23

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TRITA LWR Degree Project

The measurements should be carried out carefully in order to avoid leakages of nitrogen gas. The pressure transducer displayed a value in mV, which can be converted into mm Hg multiplying by 2.65. The transformation from the pressure in mm Hg to the conversion of nitrogen from ammonium and nitrite into nitrogen gas by Anammox bacteria in mg N/L min could be performed using ideal gas law with equation:

pmmHg ⋅ 0.012 1000  mgN  760 = ⋅ 28 ⋅ m  0.082 ⋅ T 0.025  L ⋅ min 

[17]

Where: m - nitrogen gas production, mg N/L-1 min-1 Pmm Hg - overpressure in the bottle, mm Hg 760 - conversion coefficient to convert from mm Hg to atm. 0.012 - volume of the gas phase in the bottle, L 0.082 - ideal gas coefficient R, atm L K-1 mol-1 T- temperature, K 28 - molar mass of nitrogen gas (N2) 1000 - conversion g - mg 0.025 - volume of liquid phase inside the vial, L After the transformation of each obtained pressure value using the equation. 13, results were plotted as a function of time. The average removal rate m& was calculated from the maximum slope of the curve described. This value was used for determining SAA:

 gN  m& ⋅ 0.025 ⋅ 1440 SAA  2 =  m ⋅ day  1000 ⋅ 0.00789

[18]

Where: m& - average nitrogen removal rate, mg N L-1 min-1 0.025 - volume of liquid phase inside the vial, L 1440 - number of minutes per day 1000 - conversion mg-g 0.00789 - specific surface area of 15 Kaldnes carriers, m2 After the pressure measurements, TSS and VSS were measured. The test described above assumed that all gas produced is N2, while researches underline the fact that nitric oxide and nitrous oxide can be formed. Nitrifying bacteria under low oxygen concentrations conditions usually produce these compounds. Gas tests can only serve as a rough estimation of the Anammox bacteria activity. By paying attention to the amount of produced gas and comparison with N-removal efficiency and other conditions (conductivity, pH, DO…) it is possible to get enough knowledge to evaluate the overall activity of the bacteria (Ridenoure 2004).

24

Evaluation of Deammonification process performance for supernatant treatment

Fig. 17. Pressure transducer Centrepoint Electronics 4.5.4. Deammonification Efficiency The efficiency of the Deammonification process can be determined based on the amount of NH4+-N removed (eq. 19) or it can be referred to the amount of nitrogen removed, the sum of ammonium, nitrite and nitrate (eq. 20). Eff _ NH 4 − N (% ) = +

Eff _ N (%) =

+

−

−

+

+

( NH 4 − N )in − ( NH 4 − N )out ⋅100 + ( NH 4 − N )in +

−

[19]

−

( NH 4 − N + NO2 − N + NO3 − N )in − ( NH 4 − N + NO2 − N + NO3 − N )out ⋅ 100 + − − ( NH 4 − N + NO2 − N + NO3 − N )in [20]

5. L ABORATORY SCALE D EAMMONIFICATION REACTOR The lab-scale pilot plant was built in 2001 to increase the knowledge about ammonium-rich streams with a lack of carbon source. It is located at HSRS. It was built by a group of researchers from the Department of Land and Water Resources and it consists of two Deammonification reactors. In laboratory scale pilot plant different strategies were applied during the research period. When we arrived, our initial objective was to evaluate how the pilot plant was working and try different configurations of the system. We did not look for optimal conditions or high efficiency, but to keep stable different parameters and start performing chemical analyses to get to know the process and evaluate the operation of the reactors. We started running two Deammonification reactors in October 2009 in a continuous way. From the beginning of October to the middle of November, the reactors were running with a serial configuration as they were before our arrival. After almost two months, our next step was to try to increase the activity of Anammox microorganisms by changing different operational parameters. In this period, from the middle of November to the end of December, the configuration was changed to a parallel system and both reactors were running separately. Attention was focused on different aeration strategies as a tool to increase activity and efficiency. Research studies in lab-scale pilot plant can be divided in two different periods according to the different strategy applied: • Evaluation of the reactor operation (serial system).

25

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TRITA LWR Degree Project

• Study on the optimization and influence of aeration strategy in the process performance (parallel system).

5.1. Evaluation of the reactor operation 5.1.1. Materials and Methods The lab-scale Deammonification system consisted of two serial reactors with a volume of 7.5 L (R1) and 8 L (R2), respectively (Fig 18). Influent was conducted into the first reactor (7.5 L) using peristaltic pumps that took the sewage from the inlet tank. The effluent of the first reactor was the inflow to the second reactor (8 L). Gravitational flow was used between both tanks. Both reactors were filled with Kaldnes carriers until they occupied the 40 % of the total volume in each reactor. The biomass carriers were brought from Himmerfjärden WWTP, where there is a pilot plant reactor for Anammox studies. The reactors were continuously fed with dewatered supernatant from Hammarby Sjöstadsverk digester (Table 5). The ammonium concentration was around 100 mg N-NH4+/L and COD concentration more than 1000 mg/L. Alkalinity was between 12-14 mmol/L. Conductivity in the supernatant was around 1.5 and pH value around 8. Nitrite and nitrate concentration was almost zero. Supernatant was received in tanks from Hammarby Sjöstadsverk once per month and it was stored in the fridge. Each tank was analyzed before it was employed. The supernatant had a characteristic yellow color in the beginning that turned into dark brown during its storage, probably, due to sulphate reduction to sulphide (Yang, 2009). The supernatant characteristics were not proper for Anammox bacteria growth: ammonium concentration was too low while COD was too high. Because of this reason, feeding media was made by dilution of supernatant in a proportion 1:4 with tap water to decrease COD and with an addition of NH4Cl to reach a N-NH4+ concentration in the inflow around 400 mg/L. Oxygen was supplied in both reactors with two aquarium pumps in each reactor and providing continuous aeration. Another additional pump was added as a mixer to each reactor to ensure suitable mixing and avoid sedimentation of the Kaldnes carriers. Mixing could be adjusted depending on the pumps depth in the reactor. No heater was used so temperature was kept at around 20 °C (room temperature). During the research period, the flow was fixed at 7.5 L/d, which means a hydraulic HRT around 2 days. Influent nitrogen load to the system was 2.23 g m-2 d-1 on average. This initial period lasted almost two months. Operation parameters are summarized in table 6.

Table 5. Characteristics of supernatant from Hammarby Sjöstadsverk digester. Hammarby Sjöstad

Unit

09/10/2009

09/11/2010

NH4+-N

mg/L

111

115

NO2--N

mg/L

2.96

0

NO3--N

mg/L

4.76

0

mmol/L

12.3

13.1

Alkalinity pH

-

7.96

7.95

Conductivity

mS/cm

1.40

1.52

COD

mg O2/L

1478

968

26

Evaluation of Deammonification process performance for supernatant treatment

Table 6. Operational parameters of lab-scale Deammonification reactors. Parameter

Unit

R1

Hydraulic retention time (HRT)

days

2

2

L

7.5

8

L/day

7.5

7.5

%

40

40

Reactor volume Flow Reactor filling with Kaldnes carriers

R2

Fig. 18. Lab-scale Deammonification reactors with a serial configuration. Measurements and analyses Process performance was followed up by physical measurements and chemical analyses. The process was monitored every day during the research period by performing measurements of the following physical parameters: pH, Temperature, DO, and conductivity. Flow was also checked to ensure constant load in the system. The measurements were carried out with the following manual instruments (Fig 19): • pH – WTW pH 330i together with electrode WTW SenTix 41 • Conductivity – WTW Cond 330i together with electrode WTW tetraCon 325

Fig. 19. Laboratory equipment for measuring physical parameters. 27

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TRITA LWR Degree Project

• DO – Hach Lange HQ 30d flexi together with electrode Hach Lange LDO 101 • Temperature – WTW pH 330i together with electrode WTW SenTix 41 or WTW Cond 330i together with electrode WTW tetraCon 325 The portable equipment was calibrated once a month to ensure a proper performance. Two times a week, samples were taken from the inflow tank and outflow. General chemical parameters were analyzed to follow the efficiency of the process: Ammonium, nitrite, nitrate and alkalinity. Dr Lange Tests were used for these analyses. Activity tests were done once a week and also the determination of the biomass developed on Kaldnes Rings (TSS and VSS). 5.1.2. Results and discussion Physical Parameters DO, pH, conductivity and temperature variations during the analyzed period are summarized in table 7. Graphs for DO, pH, conductivity and temperature were made to show the variation of these parameters in the influent and effluent from the reactor (Fig. 20). Based on the daily operational parameters, some results have to be discussed: a) Dissolved oxygen concentration was rather unstable in both reactors. It was supposed to be around 3 mg/L but the level was out of control several times. Probably, due to the limited aeration range of the aquarium pumps used to provide oxygen. b) pH profile shows it was stable in the influent with an average of 7.95±0.21 but pH inside both reactors was dropped down to 6 or even less. This means that nitrifying bacteria were very active and a big amount of nitrite was produced. c) Temperature was kept around 17.81±0.87 °C in R1 and 18.52±1.67 °C in R2. Both reactors were working under natural temperature of the incoming supernatant without using additional heater. For this reason, fluctuations were observed during the whole operational period.

Table 7. Variations of physical parameters in lab-scale Deammonification reactors during the operational period. Physical Parameter

Unit

Average

Min.

Max.

St. Dev.

Number of samples

mg O2/L

3.33 3.24

2.23 1.75

3.98 4.54

0.51 0.57

22 22

7.56 5.15 4.46 4.50

8.33 8.11 7.82 7.94

0.21 0.76 1.03 1.05

22 22 22 22

DO

R1 R2

pH

Inflow R1 R2 Outflow

-

7.95 6.58 5.95 6.08

Conductivity

Inflow R1 R2 Outflow

mS/c m

3.82 3.53 3.25 3.05

3.51 3.20 2.89 2.59

4.18 3.86 3.62 3.36

0.19 0.15 0.19 0.18

22 22 22 22

Temperature

R1 R2

°C

17.81 18.52

15.9 15.5

19.1 20.6

0.87 1.67

22 22

28

Evaluation of Deammonification process performance for supernatant treatment

Fig. 20. Variations of a) DO, b) pH, c) Temperature and d) Conductivity in lab-scale Deammonification reactors during the operational period.

29

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TRITA LWR Degree Project

d) Conductivity in the influent was on the average 3.82±0.19 mS/cm but during the process it was observed depletion in this value due to the removal of two ions present in the supernatant, ammonium and hydrogen. Fluctuations were observed probably due to the addition of NH4Cl to adjust NH4+ concentration in the supernatant. The Cl- present in this chemical caused and increase in conductivity. Chemical Analyses Ammonium, nitrite, nitrate and alkalinity were measured once a week in influent and effluent. Results for these analyses are presented in table 8 and fig. 21 show the changes of different parameters over time. SSupernatant composition was not constant during the research period. Ammonium concentration in the influent was rather changeable (Fig. 21 a) and that made difficult to keep a constant nitrogen load into the system despite using additional chemical (NH4Cl) to adjust the ammonium concentration. Analyses in the effluent showed that there were almost no nitrite concentration left (Fig. 21 b) while nitrate concentration was very high with an average of 40.42±10.98 mg/L (Fig. 21 b), probably due to the oxidation of some nitrite to nitrate by nitrobacter. Moreover, when Anammox bacteria used up nitrite, they produced a small amount of nitrate, according to stoichiometry. Alkalinity was not high enough for Anammox bacteria. Since the beginning of November, alkalinity in the outflow was very low. This means that Anammox bacteria had used up almost all inorganic carbon source (HCO3-). Alkalinity is closely related with pH changes. The low values of pH inside both reactors (Fig. 20 b) indicated an increase of acidity and a decrease of alkalinity as it was observed (Fig. 21 c). Nitrogen gas production SAA was checked since the 4th of October according to Dapena-Mora et al. (2007). Anammox bacteria had almost the same activity during the whole operation period. It was higher in R1 (1.784 g N/m2 d on average) than in R2 (1.433 g N/m2 d on average). Maximum activity was 1.85 g N/m2 d measured in R2. Results are presented in table 9 and fig. 22. Activity measurements can be referred not only to the biofilm area but also to the amount of VSS as it has been used for granular biomass. Results are shown in table 10 and fig. 23.

Table 8. Chemical analyses results from lab-scale Deammonification reactors during the operational period. Chemical Analyses

Unit

Average

Min.

Max.

St. Dev.

Number of samples

NH4+- N

Inflow Outflow

mg/L

445.50 293.27

319 1.34

527 411

82.81 165.24

65

NO2-- N

Inflow Outflow

mg/L

0.236

0

0.49

0.19

65

NO3-- N

Inflow Outflow

mg/L

40.2

24.7

53.2

10.98

65

Alkalinity

Inflow Outflow

mmol/ L

14.44 4.078

7.33 2.9

6.78 4.71

24.2 0.74

65

30

Evaluation of Deammonification process performance for supernatant treatment

Fig. 21. Variations of a) Ammonium, b)Nitrite and nitrate, c)Alkalinity in lab-scale Deammonification reactors during the operational period.

31

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TRITA LWR Degree Project

Table 9. SAA in g N/m2d during the operational period. R1

R2 2

Days

SAA (g N/m ·d)

SAA (g N/m2·d)

24

1.79

1.45

38

1.85

1.56

44

1.71

1.29

Fig. 22. SAA referred to the biofilm area. Table 10. SAA in g N/gVSS d during the operational period. R1

R2

Days

SAA (g N/gSVV·d)

SAA (gSVV·d)

24

0.040

0.032

38

0.044

0.042

44

0.041

0.035

Fig. 23. SAA referred to the amount of VSS. Removal Efficiency Total nitrogen removal efficiency and also ammonium removal efficiency were calculated (Table 11). The system worked efficiently at the beginning of the research period. Total nitrogen removal efficiency was over 80 % (Fig 24). Although after less than 10 days, the efficiency dropped down to less than 20 %, probably due to the low alkalinity and fluctuations on the DO level. Afterwards, nitrogen removal efficiency was varying between 15 % and 25 % during the rest of the operational time. 32

Evaluation of Deammonification process performance for supernatant treatment

Table 11. Total nitrogen and ammonium removal efficiency of labscale Deammonification reactors. Removal efficiency Total Nitrogen Ammonium

Unit

%

Average

Min.

Max.

St. Dev.

Number of samples

31.6

16.7

82.9

28.7

5

41.0

22.0

99.6

32.8

5

Fig. 24. Total nitrogen and Ammonium removal efficiency of lab-scale Deammonification reactors Results from SAA showed that Anammox bacteria did not experienced this drop in their activity during the first days. The reason could be that the low nitrogen removal efficiency achieved was not only due to Anammox bacteria. 5.1.3. Conclusions • Supernatant from Hammarby Sjöstad was not suitable for carrying out the Deammonification process due to its low ammonium content, low alkalinity and high COD content. • Physical parameters can be used as a tool to monitor and control the Deammonification process. • In one-step partial nitritation/Anammox system, DO level has to be controlled and kept on proper level to ensure favorable conditions for running both processes. • DO level was the most unstable parameter with big fluctuations. Suitable equipment and control on the oxygen level is required to optimize Deammonification process performance. • DO level and nitrite concentration seem to be key factors for the Anammox reaction and efficiency of the process. • Partial nitration/Anammox can be applied at lower temperature than the optimal value. • Low efficiency of nitrogen removal varying between 15 and 25 % was obtained during the whole experimental period. • No significant changes in SAA with an average of 1.784 g N/m2 d (R1) and 1.433 g N/m2 d (R2) were observed. 33

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

• Influence of the ions present in the liquid of reaction on the conductivity value was found. • Profiles of nitrogen forms could be used as a tool to follow and monitor the process performance. • Optimization of the process performance by changing operational parameters turned out to be necessary.

5.2. Study on the optimization and influence of aeration strategy on the process performance Knowledge about the microorganisms involved in biological wastewater treatment and their response to different operating conditions is essential to optimize the process performance. Intermittent aeration has been applied successfully to optimize nitrogen removal using digested swine manure with a low Carbon/Nitrogen ratio and high ammonia concentration (Mota et al., 2005). During this period, intermittent aeration was tested in lab-scale Deammonification reactors in order to study the influence in the process performance. Apart from the new aeration strategy, other changes were applied to optimize the system. 5.2.1. Materials and Methods In this second period, from the middle of November to the end of December, the two Deammonification reactors were running separately (Fig 25). Capacity of the first reactor (R1) was increased changing the volume until 10 L. The second reactor (R2) kept its volume of 8 L. Despite their different capacity, the volume of wastewater was 7.5 L in each reactor. Both reactors were operated as a parallel system using the same feeding media. Flow to the reactors was provided using peristaltic pumps from the inflow tank. Both reactors were filled with Kaldnes carriers up to 40 % of their total volume. The biomass carriers were taken from Himmerfjärden WWTP. Feeding media to the reactors was changed and both of them were supplied continuously with supernatant also from Himmerfjärden WWTP, which had higher ammonium concentration, around 1200 mg/L, and low organic matter content.

Fig. 25. Lab-scale Deammonification reactors with a parallel configuration.

34

Evaluation of Deammonification process performance for supernatant treatment

Table 12. Characteristics of supernatant from Himmerfj채rden WWTP. Supernatant from Himmerfj채rden

Unit

26/11/2009

NH4+-N

mg/L

1240

NO2--N

mg/L

0

NO3--N Alkalinity

mg/L

2.94

mmol/L

88.6

-

8.09

pH Conductivity

mS/cm

8.5

COD

mg O2/L

665

Supernatant was brought in tanks and stored in the fridge. During the experimental period it was noticed that ammonium concentration and acid capacity experienced little changes over time. Probably it was because of the digestion of the organic material present in the reject water and its exposure to the air. Composition of each tank was analyzed before its use and the values for this supernatant are presented in table 12. Himmerfj채rden supernatant characteristics were more suitable for carrying out the Deammonification process. Ammonium concentration in inflow was fixed around 850 mg/L by dilution of the fresh supernatant with tap water but no additional ammonium source was necessary due to its high ammonium concentration. Also, the low content of biodegradable organic carbon in the feeding media avoided an excessive growth of heterotrophic bacteria. In this case, intermittent aeration was tested in both reactors connecting timers to the pumps but using different aeration strategies. The parallel system allowed trying two different strategies at the same time. In the first reactor (R1), aeration cycle was 30 minutes aeration followed by 15 minutes without aeration while in the second reactor (R2) oxygen supply lasted for 30 minutes and it was switched off during another 30 minutes. Oxygen level was kept at around 3 mg/L. Mixing of the Kaldnes carriers was provided with air supply from the bottom of the reactors to avoid sedimentation of the carriers. Moreover, heaters were added in each reactor to reach a temperature inside the reactors around 27 째C to keep favorable conditions for bacteria growth. HRT was fixed in 2 days with an average flow of 7.5 L/d for both reactors. During the research period, influent nitrogen load to the system was 2.126 g m-2 d-1 on average. Operational parameters are summarized in table 13.

Table 13. Operational parameters of lab-scale Deammonification reactors. Parameter

Unit

R1

R2

Hydraulic retention time (HRT)

days

2

2

L

10

8

Reactor volume Flow

L/day

3.75

3.75

Reactor filling with Kaldnes carriers

%

40

40

Duration of the period with aeration

min

30

30

Duration of the period without aeration

min

15

30

-

0.5

1

Ratio no aeration/aeration

35

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TRITA LWR Degree Project

Measurements and analyses During the analyzed period, process performance was followed up by physical measurements and chemical analyses. Physical parameters (pH, Temperature, DO, conductivity and Redox potential) were monitored almost every day. Flow was also checked daily to ensure constant loading into the system. The measurements were carried out with the following manual instruments: • pH – WTW pH 330i together with electrode WTW SenTix 41 • Conductivity – WTW Cond 330i together with electrode WTW tetraCon 325 • DO – Hach Lange HQ 30d flexi together with electrode Hach Lange LDO 101 • ORP – WTW pH 330i with electrode Hamilton Polyplast ORP P/N 238385/01 • Temperature – WTW pH 330i together with electrode WTW SenTix 41 or WTW Cond 330i together with electrode WTW tetraCon 325 Two times a week, samples were taken from the inflow tank, outflow and inside the reactors. General chemical parameters were analyzed to follow the efficiency of the process: ammonium, nitrite, nitrate and alkalinity. Dr Lange Tests were used for these analyses. Activity Tests were done once a week and also the determination of the biomass developed on Kaldnes carriers (TSS and VSS). Moreover, biofilm thickness was observed. 5.2.2. Results and discussion Physical Parameters DO Dissolved oxygen concentration was measured carefully inside both reactors over the research period. It is a critical parameter for the partial nitrification/Anammox process because it is the main limiting factor; during partial nitrification, oxygen is demanded to produce nitrite but oxygen is also responsible for the inhibition of the Anammox process.

Fig. 26. Oxygen profiles during intermittent aeration for reactors R1 and R2 (11.30.2009)

36

Evaluation of Deammonification process performance for supernatant treatment

Table 14. DO variations of lab-scale Deammonification reactors during the aeration period. Dissolved oxygen

Unit

Average

Min.

Max.

St. Dev.

Number of samples

R1

mg O2/L

2.18

0.05

3.65

0.74

10

R2

mg O2/L

2.01

0.09

3.11

0.91

10

To control oxygen level supply, intermittent aeration was installed in both reactors. Two different aeration strategies were studied: 30 minutes aeration with 15 minutes without aeration in R1 and 30 minutes aeration followed by another 30 minutes without aeration in R2 (Fig. 26). Maximum DO level in each reactor was controlled every day and three times a week the detailed DO profile was measured. Maximum level of DO during the aeration period was kept around 3 mg/L. When the aeration starts, DO level increases quickly and when aeration stops, DO level decreases at the same rate until DO level is zero. During the period of the study, the DO profile was difficult to be kept stable due to the manual regulation and the short range of oxygen supply from the pumps. For this reason, profiles were checked twice a week and their evolution is shown in Appendix II. The average oxygen concentration during the aeration period was 2.18±0.74 mg O2/L with a maximum of 3.65 mg O2/L in R1 and 2.01±0.91 mg O2/L with a maximum of 3.11 mg O2/L in R2 (Table 14). pH pH value was measured in the inflow tank and in outflow of both reactors. It was not controlled inside the reactors because it was usually the same value as in the influent (Siegrist et al., 1998). During the analyzed period, pH in the influent was rather stable on the average 8.14±0.11 and there was no necessity of adjusting pH value by dosage of chemical substances. pH value was lower in the effluent of both reactors (equal to 7.11±0.65 in R1 and 7.31±0.59 in R2). It is known that during the partial nitritation a drop in the pH value is expected while a rise of pH is observed when the Anammox reaction takes place (Cema, 2009). For this reason, performance of both processes in a single stage resulted in a minimal drop in pH (Fig. 27). Besides, pH value should be checked for high ammonium concentration streams because a high pH value can cause inhibition of Nitrobacter by free ammonia (Anthonisen, 1976). pH was kept under 8.5 during the whole operation period (Table 15). Detailed values are presented in Appendix II.

Table 15. pH variations of lab-scale Deammonification reactors during the research period. pH

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Inflow

-

8.14

7.91

8.37

0.11

16

Outflow R1

-

7.12

5.79

7.79

0.55

16

Outflow R2

-

7.32

5.74

8.28

0.56

16

37

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TRITA LWR Degree Project

Fig. 27. Variation of pH of lab-scale Deammonification reactors during the operational period. Conductivity The process has also been monitored by conductivity measurements in the influent and in the effluent from both reactors. Conductivity can be measured quickly and easily and this is the main reason for its use as a monitoring tool. Nitritation and Anammox processes cause a depletion in conductivity due to the removal of ammonium and hydrogen, two ions present in the supernatant (Fig. 28). During the operational period, conductivity in the influent was on the average 6.47Âą0.60 mS/cm Table 16). Difference between conductivity values in inflow and outflow was 4.14 mS/cm for R1 and 4.26 mS/cm for R2 on average. Inflow and outflow conductivity curves have the same tendency. Specific values are shown in Appendix II.

Table 16. Conductivity variations of lab-scale Deammonification reactors during the research period. Conductivity

Unit

Inflow Outflow R1

mS/cm

Outflow R2

Average

Min.

Max.

St. Dev.

Number of samples

6.47

4.90

7.61

0.60

17

2.33

1.50

4.43

0.91

17

2.21

0.88

4.25

0.99

17

Fig. 28. Variation of conductivity of lab-scale Deammonification reactors during the operational period. 38

Evaluation of Deammonification process performance for supernatant treatment

Fig. 29. Variation of temperature of lab-scale Deammonification reactors during the operational period.

Table 17. Temperature variations of lab-scale Deammonification reactors during the research period. Temperature R1 R2

Unit °C

Average

Min.

Max.

St. Dev.

Number of samples

27.12

25.5

29.5

1.04

17

27.14

26.1

30.1

1.06

17

Temperature Temperature is a key factor for the biological processes. At the beginning, temperature was fixed around 30°C using a heater but later it was decreased and kept in an average value of 27°C in both reactors, this is, under mesophilic conditions (Table 17). Despite the optimal temperature for Anammox process is around 37°C, it was proved that this process can be operated at a temperature below 30°C (Szatkowska et al., 2006) with the consequent savings on heating. This decrease in temperature (Fig. 29) step by step resulted in a slight decline of removal rates but later bacteria were able to adapt to the new conditions and recover its efficiency. More detailed data is presented in Appendix II. Redox potential Redox potential was measured in inflow and outflow from the reactors. ORP value is dependent on the DO level and temperature. It has been reported that in low DO concentrations, changes in redox potential occur due to different biochemical conditions (Holman & Wareham, 2003). For the process controlling, the change on redox potential was more important that the absolute value. It has been realized that the process during the operational period took place at different absolute values but showed the same tendency in ORP change.

39

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TRITA LWR Degree Project

Table 18. Redox potential variations of lab-scale Deammonification reactors during the research period. Redox potential

Unit

Inflow Outflow R1 Outflow R2

mV

Average

Min.

Max.

St. Dev.

Number of samples

-66.87

-286.5

-7.1

60.51

17

72.89

-34

180.1

50.56

17

48.04

-43.7

141.2

40.88

17

Fig. 30. Variation of Redox potential of lab-scale Deammonification reactors during the operational period. Redox potential in inflow was rather lower due to the oxidizing ability of the solution. After the aeration periods, ORP in the outflow from both reactors increased (Fig. 30). Redox potential was an unstable parameter with a big fluctuation between the maximum and minimum value (Table 18). Details are presented in Appendix II.

Fig. 31. Redox profiles during intermittent aeration for reactors R1 and R2 (12.03.09). 40

Evaluation of Deammonification process performance for supernatant treatment

Redox profiles inside the reactors were also performed parallel to DO profiles to see the variations in redox during aeration/non aeration periods. ORP profiles follow the same trend but different absolute values (Fig 31). When aeration starts in the reactors, nitrifying bacteria oxidize ammonia to nitrites. This process is followed by an increase of Redox potential. When the aeration stops, it can be observed a decrease in Redox potential due to an increase in the concentration of reduced forms. Redox profile was checked weekly and results are presented in Appendix II. Chemical Analyses NH4+-N concentration Ammonium concentration was measured in inflow and outflow from both reactors (Table 19). The NH4+-N load in inflow was controlled to keep the concentration at around 850 mg/L because with high nitrogen load, streams are difficult to treat biologically. No other forms of inorganic nitrogen were analyzed in influent. Ammonium concentration in effluent was lower in R2 (Fig 32), which means higher ammonium removal efficiency in this reactor. Detailed values are presented in Appendix II.

Table 19. Ammonium concentration in lab-scale Deammonification reactors during the research period. [NH4+-N]

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Inflow

mg/L

850.3

820

897

23.87

10

Outflow R1

mg/L

117.12

5.92

272

86.32

7

Outflow R2

mg/L

108.5

36.6

252

77.35

7

Fig. 32. Variations of Ammonium concentration in lab-scale Deammonification reactors during the operational period.

41

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Table 20. Nitrite concentration in lab-scale Deammonification reactors during the research period. [NO2--N] Outflow R1 Outflow R2

Unit mg/L

Average

Min.

Max.

St. Dev.

Number of samples

3.54

2.13

5.64

1.06

7

6.70

4.87

10.3

1,82

7

Fig. 33. Variations of Nitrite concentration in lab-scale Deammonification reactors during the operational period. NO2--N concentration Nitrite concentration is a limiting factor for the partial nitritation/Anammox process. Deficient nitrite production can suppress the reaction but also an over concentration inhibits the Anammox process. A ratio of nitrite-to-ammonium that exceeds 2 causes an important decrease on the efficiency (Cema, 2009). Nitrite was almost zero in inflow, so it was measured only in outflow from both reactors. Nitrite concentration values are presented in table 20 and fig. 33 shows the variations in NO2--N profile during the operational period. Detailed values are presented in Appendix II. NO3--N concentration Nitrate concentration was measured just in outflow from both reactors because there were no nitrates in the influent. During the process, nitrate was the main compound in outflow while nitrite and ammonium were almost consumed. The nitrate production was around 11.44 % on average of the removed ammonium for R1. This value is very close to the theoretical one of 11 % taking into account the stoichiometry. Differences between theoretical and experimental values are higher in R2 with an average of nitrate production of 5.35 %. This can be caused by the presence of heterotrophic denitrifying bacteria. The percentage of nitrate production to ammonium consumption is shown in fig. 34 for both reactors.

42

Evaluation of Deammonification process performance for supernatant treatment

Table 21. Nitrate concentration in lab-scale Deammonification reactors during the research period. St. Dev.

Number of samples

[NO3--N]

Unit

Average

Min.

Outflow R1

mg/L

77.78

2.35

108

38.28

7

Outflow R2

mg/L

34.23

4.38

54.5

20.99

7

Max.

Fig. 34. Evolution of Nitrate production in % in lab-scale Deammonification reactors.

Fig. 35. Variations of Nitrate concentration in lab-scale Deammonification reactors during the operational period. Additionally, nitrite concentration values are presented in table 21 and fig. 35 shows the variations in NO3--N profile during the operational period. Detailed values are presented in Appendix II. Alkalinity The control of the alkalinity is important to guarantee the buffer capacity of the water system and because a lack of alkalinity can inhibit nitrifying bacteria and decrease nitritation rates. It was measured in both influent and effluents of the reactors. Alkalinity values in inflow were stable with an average of 58.83Âą6.72 mmol/L (Table 22). Despite a decrease of alkalinity that was observed in outflow of both reactors, no lack of this parameter was noticed (Fig. 36). Detalied values are presented in Appendix II.

43

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TRITA LWR Degree Project

Table 22. Alkalinity variations in lab-scale Deammonification reactors during the research period. Alkalinity

Unit

Inflow Outflow R1

Average

Min.

Max.

St. Dev.

Number of samples

58.83

52.8

67.6

6.72

6

6.27

0.97

19.1

6.60

6

8.11

4.1

14.7

4.47

6

mmol/L

Outflow R2

Fig. 36. Variations of alkalinity in the lab-scale Deammonification reactors during the operational period. Decrease of alkalinity observed is explained by the fact that 2 mol of alkalinity are required for oxidation of 1 mol NH4+ to NO2-. Moreover, the consumption of alkalinity resulted in a decrease in the pH value which prevents excessive nitrate production. Correlation between Ammonium concentration and conductivity It was found a dependency between NH4+-N concentration in influent and conductivity values of the supernatant (Fig 37). Both curves run parallel as conductivity value is proportional to the analyzed concentration of ammonium. Experimental correlation between these two parameters was done ignoring the presence of other ions in supernatant that can affect the total measured conductivity (Fig 38).

Fig. 37. Ammonium concentration and conductivity in the influent in lab-scale Deammonification reactors. 44

Evaluation of Deammonification process performance for supernatant treatment

Fig. 38. Correlation between Ammonium concentration and conductivity in the influent in lab-scale Deammonification reactors.

Table 23. Biomass developed on Kaldnes carriers R1

R2

Days

TSS (g/L)

VSS (g/L)

TSS (g/L)

VSS (g/L)

1

14.70

12.96

14.70

12.96

7 13 22

14.86 15.43 15.48

13.11 13.32 13.79

15.18 15.55 15.60

12.97 13.87 13.89

Fig. 39. VSS from Kaldnes carriers from lab-scale Deammonification reactors. Biomass measurements The determination of the biomass attached to Kaldnes carriers was calculated using the procedure described in Standard Methods, 1999 (Table 23). VSS represent the amount of biomass attached to the rings. In this case, it refers to nitrifying, Anammox and also denitrifying bacteria. The increase of these values during the analyzed period means a progressive growth in the bacteria population (Fig 39). In fact, an increment of the biofilm thickness was noticed due to the enrichment of the biomass in the system. It also means that there is no wash-out of the bacteria 45

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population from the system. It was observed that nitrogen removal rate was increasing with the rise of VSS concentration and that nitrogen removal rate was higher in R2. Probably, it can be connected with a bigger amount of biomass in the biofilm. Suspended Solids in Supernatant During the research period, some problems were noticed connected with the high concentration of suspended solids (SS) in effluent; although no specific measurements were done in this period. Bacterial activity measurements Specific Anammox Activity SAA tests were carried out adapting the words of Dapena-Mora et al. (2007). Following this methodology, the activity measured is the maximum activity of Anammox bacteria without substrate limitations for the range of ammonium and nitrite employed, being actually a potential activity. Both reactors were operated obtaining high Anammox activity with an average value for the R1 of 2.116 g N/m2 d and 2.377 g N/m2 d for R2 (Table 24). However, a loss of bacteria activity was observed on the 7th day, probably due to the decrease in temperature (Fig 40). Later, the activity increased again during the operation period. Maximum activity was 2.812 g N/m2 d measured in R2. Activity measurements were referred not only to the biofilm area but also to the amount of VSS. Results are shown in table 25 and fig. 41: Anammox activity was always higher in R2, probably due to the aeration strategy. The high Annamox activity obtained during the tests caused the accumulation of nitrogen gas between the rings. Therefore, it was observed that rings were floating inside the bottles during the tests. These tests serve as an estimation of the potential Anammox bacteria activity.

Table 24. SAA in g N/m2 d during the operational period. Days 1 7 13 22

R1

R2

SAA (g N/m2·d) 2.231 1.880 2.241 2.114

SAA (g N/m2·d) 2.343 2.038 2.315 2.812

Fig. 40. SAA referred to the biofilm area.

46

Evaluation of Deammonification process performance for supernatant treatment

Table 25. SAA in g N/gVSS d during the operational period. R1

R2

Days

SAA (g N/gVSS·d)

SAA (g N/gVSS·d)

1

0.054

0.057

7

0.045

0.050

13

0.053

0.053

22

0.048

0.064

Fig. 41. SAA referred to the amount of VSS. Deammonification process activity It is also useful to calculate the Deammonification activity of the process under the specific operational conditions. It refers to the nitrogen removal rate in g N/m 2 d and it depends on how efficient is the system to produce the necessary NO2- to carry out the process. It can be calculated as follows: (( NH 4 + − N + NO2 − − N + NO3− − N )in − ( NH 4 + − N + NO2 − − N + NO3− − N )out ) ⋅ F  gN  1000 Deam. Activity  2  = Vreal ⋅ 40%  m ⋅d  ⋅ 500 1000

[21] Where, F - flow to the reactor, L/d 1000 - conversion mg-g Vreal - volume of the reactor, L 40% - percentage of Kaldnes rings in the reactor volume 1000 - conversion L-m3 500 - effective specific surface area, m2/m3 Results are shown in table 26: As it was expected, SAA were always higher than the Deammonification activity value (Fig. 42 and 42). In this way, comparing both values it is possible to evaluate the overall activity of the bacteria and the performance of our system.

47

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Table 26. Deammonification process activity in g N/m2 d during the operational period. R1 Days

Deammonification activity (g N/m2·d)

1 7 13 22

2.038 1.699 1.460 1.647

R2 Deammonification activity N/m2·d)

(g

1.940 1.875 1.584 1.857

Fig. 42. Comparison between SAA and Deammonification activity in R1.

Fig. 43. Comparison between SAA and Deammonification activity in R2. Both reactors were running with a nitrogen load of 2.156 g N/m2 d on average. Considering the influent load, it is also possible to evaluate the difference between the influent nitrogen load and the Deammonification process activity (Fig 44). This difference represents the amount of nitrogen that was not removed. The removal rate was 1.711 g N/m2 d for R1 and 1.814 g N/m2 d for R2 on average. It can be observed that nitrogen removal rate decreased after the 7th day and increased again after 15 days. This can be due to the adaptation of the bacteria. The specific Anammox activity (Table 24) showed the same tendency over time. 48

Evaluation of Deammonification process performance for supernatant treatment

Fig. 44. Comparison between nitrogen removal rate and nitrogen load in the influent. Removal Efficiency Efficiency can be calculated in % taking the compounds measurements for the analyses during the research period as it was described in chapter 3.4.4. It can be expressed based on the total amount of nitrogen removed or only on the NH4+-N removed. Both reactors were operating steadily with a high efficiency. The total inorganic nitrogen removal during the research period was 77.0±0.2 % in R1 and 82.9±0.1 % in R2 whereas ammonium removal was 86.4±0.1 % in R1 and 87.5±0.1 % in R2 on average (Table 27 and 28). The lost of bacteria activity after 7 days resulted in a decrease in the removal efficiency (Fig. 45 and 46). Detailed values are presented in Appendix II.

Table 27. Total nitrogen removal efficiency of lab-scale Deammonification reactors. Total nitrogen removal efficiency R1 R2

Unit

%

Average

Min.

Max.

St. Dev.

Number of samples

77.0

59.1

93.0

0.2

7

82.9

65.4

90.6

0.1

7

Fig. 45. Total nitrogen removal efficiency of lab-scale Deammonification reactors. 49

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Table 28. Ammonium removal efficiency of lab-scale Deammonification reactors. Ammonium removal effciency R1 R2

Unit

%

Average

Min.

Max.

St. Dev.

Number of samples

86.4

69.7

99.3

0.1

7

87.5

71.9

95.6

0.1

7

Fig. 46. Ammonium removal efficiency of lab-scale Deammonification reactors. Surprisingly, the progressive increase over time in biofilm thickness (Fig. 39) was not followed by a gradual rise of nitrogen removal efficiency. In fact, during the first 10 days, both total nitrogen and ammonium removal decreases. It means that there were other parameters like DO, temperature and nitrogen load influencing nitrogen removal in the reactor. It could be caused by an increase of nitratation due to a high DO level in the reactors. Concentration of nitrates in the outflow increased in this period (see Fig. 35). After these first days, total efficiency increased again until a maximum value of around 90 %. In fact, a stable nitrogen removal with a continuous gas production was observed. Total inorganic nitrogen removal was always higher in R2 during the operational period, probably due to the aeration strategy and a higher activity of the bacteria population. At the same time, ammonium removal was always higher than total inorganic nitrogen removal which means that there is still ammonium concentration in the outflow from both reactors. 5.2.3. Conclusions • Supernatant coming from Himmerfjärden WWTP showed better quality to carry out the Deammonification process due to its high ammonium content, low COD content and high alkalinity. • The use of intermittent aeration is a good choice to create properly oxygen conditions to ensure the co-existence of both nitrifiers and Anammox bacteria in the biofilm and increase the process efficiency. • Two aeration strategies were tested: 30 minutes aeration followed by 15 minutes without aeration and 30 minutes aeration followed by another 30 minutes without aeration. It was proved that the second strategy was better. In fact, this is the aeration strategy used in Himmerfjärden Full-scale Anammox reactor.

50

Evaluation of Deammonification process performance for supernatant treatment

• Physical parameters such as conductivity, pH or Redox potential can be used as a tool to monitor and control the Deammonification process. • Alkalinity change during the Deammonification process can be a supporting measurement to control the one-step partial nitritation/Anammox process. • Necessity of on-line control of physical parameters (especially DO) to get reliable and quick data about the changes of the process performance was found. • Redox potential was the most unstable parameter and its changes are dependent on the DO level. • Conductivity was indicated as a physical parameter that enables to estimate the process efficiency without performing chemical analyses. • Both reactors were operating with high nitrogen removal efficiency. Maximum nitrogen removal efficiencies were 93% in R1 and 90.6% in R2. • High Anammox activity was measured in the biomass from both reactors. The average value was 2.116 g N/m2 d in R1 and 2.377 g N/m2 d for R2. Higher activity in R2 was due to the better aeration strategy. • Time is necessary for the process recovery in case of the lost of bacteria activity. • The increase of the biofilm thickness evidenced a progressive growth in the bacteria population over time.

6. B ATCH EXPERIMENTS WITH INTERMITTENT AERATION During December, parallel to the monitoring and control of the Deammonification process operation, several number of batch experiments using different strategies of aeration were carried out to study in detail the changes in physical parameters and the variation in the concentration of different nitrogen compounds in the reaction period (4-4.5 hours). With these batch experiments, where lab-scale conditions were simulated, the aim was to determine the best strategy of aeration and oxygen condition for partial nitrification/Anammox process.

6.1. Materials and methods Plastic vessels were used as batch reactors (Fig 47). Each vessel was filled with a fixed volume of supernatant from Himmerfjärden WWTP diluted with distilled water to reach the desired concentration of ammonium in the beginning of the experiment. The vessel was inside a thermostatic bath to keep the temperature at 25 °C, and the dissolved oxygen in it was removed until it reached less than 1 mg/L using a nitrogen gas line. A fixed amount of Kaldnes carriers with biomass attached were taken randomly from R2 and added, previously washed with diluted supernatant. A magnetic stirrer was employed to ensure complete mixing of the reaction medium. A determinate concentration of oxygen was supplied into the vessel during the aeration stage and DO, Redox, pH and conductivity were measured during the whole experiments. All cycles began with aeration period.Using a syringe, liquid samples were taken from the vessel each time that aeration ended and started, and every 30 min in the continuous aeration experiments. Samples were filtrated in laboratory using a 1.6 µm pore size prefilter followed by a 0.45 µm pore size filter.

51

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Fig. 47. Scheme of the experimental equipment to follow up the batch experiments (Malovanyy, 2009). The initial and final samples were immediately analyzed for nitrogen forms, alkalinity, COD and Total Nitrogen (TN) the same day of the experiment and frozen la-ter, while the intermediate samples were directly frozen. Batch experiments were carried out using biomass with the same characteristics to allow comparison between the results obtained. After the experiments, SAA, TSS and VSS were measured. The groups of batch experiments performed using different strategies of aeration are summarized in table 29:

6.2. Results and discussion 6.2.1. Group I The first group of experiments were done out the 1st of December to get in touch with the experimental equipment and improve methodology.

Table 29. Batch experiments summary. Group o

N experiment

I (01/12/2009) 1

2

DO (mg O2/L)

Cycle duration (min)

3

4

0

1/3

3

No aeration/aeration ratio No aeration/aeration duration (min)

II (15,16 & 17/12/2009) 5

6

7

8

1

3

0

1/3

2

0.5 15/30

30/60

45

90

9

10

11

12

1

3

0

1/3

3

13

14

1

3

4

- 15/45 30/30 45/15 - 15/45 30/30 45/15

--

15/45 30/30 45/15

60

60

60

4.5

4

4

4

1

1

1

1

Initial concentration of NH4+-N (mg/l)

130

~150

~150

~150

Volume of Kaldness rings (mL)

400

400

400

400

Total duration (h) Volume of supernatant (L)

SAA (25°C) 2 (g N/m ·d)

2.033

2.286

52

Evaluation of Deammonification process performance for supernatant treatment

Table 30. Chemical analyses Group I. NH4+-N NO2--N NO3--N Alkalinity COD TN N removal

Unit

Inflow

Outflow Exp. 1

Outflow Exp. 2

mg/L mg/L mg/L mmol/L mg O2/L mg/L %

130.0 0.19 7.6 5.75 80.8 141.5

66.7 2.43 15.8 38.4

67.9 1.42 15.6 0.90 85.4 92.0 38.4

Two batch experiments were carried out at the same time and under the same conditions in 1L working capacity vessels and they lasted 4.5 h. The only difference between them was the duration of the cycle, being 45 min in the experiment 1 and 90 in experiment 2. Nitrogen forms were measured as well as COD and alkalinity. Although the difference in the cycle duration, the concentrations of nitrogen forms in the liquid are similar, reaching the 38.4% of efficiency in both experiments (Table 30). During experiments it was considered the possibility to increase the operation capacity using vessels with 2 L of volume. However, because of the difficulties to have a homogeneous mixing, it was decided to keep the initial volume. 6.2.2. Group II This group of experiments was performed during three consecutive days, using each day the same strategies of aeration but changing the concentration of dissolved oxygen. Four aeration strategies were performed each day. The ratios of no aeration/aeration were 0, 1/3, 1 and 3, which corresponded with the following durations of no aeration/aeration periods (Table 31). A study by Cema et al. (2008) reported studies about the optimum DO concentration level in a range from 0.5 to 4 g O2 m-3 for continuous aeration. In our case, three different DO levels were tested: 2, 3 and 4 mg/L.

Table 31. Aeration strategies used during batch experiments. Group II. Period without aeration (min) 0 15 30 45

Ratio 0 1/3 1 3

Period with aeration (min) 60 45 30 15

Cycle duration (min) 60 60 60 60

Table 32. Chemical analyses for different aeration ratios, DO=2mgL. R=0 Unit

Inflow

NH4+-N

mg/L

NO2--N

mg/L

NO3--N

R=1/3

Outflow

Inflow

154.8

92.1

0.29

2.99

mg/L

0.22

Alkalinity

mmol/L

COD TN N removal

R=1

R=3

Outflow

Inflow

Outflow

Inflow

Outflow

152.1

67.8

149.1

100.2

148.3

109.0

0.67

3.40

0.36

1.10

0.75

0.74

4.09

1.14

8.00

0.36

2.24

1.06

1.20

11.6

7.3

-

5.6

-

8.2

-

8.4

mg O2/L

81.8

93.1

-

82.8

-

77.8

-

82.2

mg/L

154

97

-

78

-

99

-

%

36.2

48.5

53

30.9

113 26.1

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Table 33. Chemical analyses for different aeration ratios, DO=3mgL. R=0

R=1/3

R=1

R=3

Unit

Inflow

Outflow

Inflow

Outflow

Inflow

Outflow

Inflow

Outflow

NH4+-N

mg/L

157.4

87.7

153.6

61.4

155.3

99.9

148.8

100.8

NO2--N

mg/L

0.77

3.67

0.75

4.09

0.72

1.30

1.14

0.75

mg/L

0.34

6.17

1.28

9.22

0.45

3.63

1.25

2.79 7.9

NO3--N Alkalinity

mmol/L

10.7

2.0

-

4.6

-

2.8

-

COD

mg O2/L

74.2

86.6

-

86.5

-

91.2

-

84

TN

mg/L

155

364

-

77

-

102

-

105

N removal

%

38.4

52.0

33.0

31.0

Table 34. Chemical analyses for different aeration ratios, DO=4mgL. R=0

R=1/3

R=1

R=3

Unit

Inflow

Outflow

Inflow

Outflow

Inflow

Outflow

Inflow

Outflow

NH4+-N

mg/L

152.7

44.7

157.8

30.3

149.7

94.8

150.4

94.4

NO2--N

mg/L

0.89

5.37

0.99

5.55

0.63

1.36

0.90

0.93

NO3--N

mg/L

0.68

11.87

0.85

12.99

0.32

4.33

0.81

4.06

Alkalinity

mmol/L

11.6

3.6

-

2.5

-

5.3

-

8.2

COD

mg O2/L

81.8

80.5

-

91.6

-

75.3

-

84.5

TN

mg/L

154

66

-

56

-

102

-

N removal

%

59.9

69.5

33.3

104 34.7

After analyzing the samples, the results listed in tables 32, 33 and 34 were obtained for different DO concentrations. An increase in DO concentration leads to the decreasing of ammonium content in effluent (Fig 48 a). Moreover, the higher the oxygen concentration and aeration period, the greater nitrite and nitrate production, because of the nitritation step taking place (Fig. 48 b and 48 c). With DO concentration of 4 mg/L, a pronounced increase of nitrite and nitrate were observed. The overall inorganic nitrogen reduction seems to be very similar with the different DO supplies and for the ratios 1 and 3 (Fig. 48 d), and better in the experiment performed with an aeration ratio of 1/3. The efficiency of Deammonification can be calculated using equations 19 and 20 (Fig. 49). The efficiency of nitrogen removal in the Anammox process depends on nitrite formed in the first step of the Deammonification process, the partial nitritation. The results of the 12 batch experiments performed in different conditions show that the highest efficiency was obtained for a dissolved oxygen concentration of 4 mg/L and a no aeration/aeration ratio equal to 1/3 (exp. no 12), with a nitrogen removal efficiency of the 69.5 % (Fig. 49). The concentration of dissolved oxygen and the ratio of aeration have a very strong influence on the nitrogen removal rates and efficiency of the Deammonification process. Taking into account the best strategy obtained, concentration of nitrogen forms during experiment no 12 were analyzed from the frozen samples by Flow Injection Analysis (FIA) based on using VIS spectrophotometry AQUATEC-TECATOR 5400 ANALYZER (Fig. 50). Detailed data is presented in Apppendix III. 54

Evaluation of Deammonification process performance for supernatant treatment

Fig. 48. a) Ammonium concentration b)Nitrite concentration c)Nitrate concentration d) Mineral N concentration for different aeration ratios and oxygen supply at the end of the batch experiments. 55

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Fig. 49. Efficiency of ammonium (a) and nitrogen (b) removal for different aeration rates and oxygen supply. During the Deammonification process, part of the ammonium oxidizes to nitrite that reacts with remaining ammonium to produce nitrogen gas due to Anammox bacteria in the period without aeration. The oxygen supplied is consumed in the outer part of the biofilm where nitrite is produced by nitrifying bacteria so Anammox bacteria are protected from it. Nitrate is also produced, in an amount depending on the concentration of dissolved oxygen. The presence of the two steps that occur in the Deammonification process can be confirmed: the partial nitritation in the aeration stage and the Anammox reaction during the anaerobic operation. The ammonium concentration decreases continuously in aeration stages due to the partial nitrification and during the periods without aeration because of the Anammox reaction, being this drop faster during aeration stages. Nitrite variation has an oscillating behavior, increasing during aeration stages due to ammonium oxidation by Nitrosomonas, and decreasing during non aerated stages, when Anammox reaction takes place. The values were kept between 5.5 and 9.7 mg/L during the whole reaction period. Nitrate is produced and its concentration at the end of the experiment was 14 mg/L. The rate of nitrate production is higher during the aeration period.

56

Evaluation of Deammonification process performance for supernatant treatment

Fig. 50. Ammonium, nitrite and nitrate variation for experiment no 12 (DO=4mg/L and R=1/3).

Fig. 51. Partial efficiency in aeration-no aeration periods for DO=4mg/L and R=1/3. The partial efficiencies of nitrogen removal in each period can be calculated. It can be noticed that more nitrogen is removed during aeration periods, being the value higher over time. Besides chemical analyses, physical parameters were also controlled during the experiments to monitor the process. Profiles of DO and Redox have been done as well as control of pH and conductivity. Value of temperature was constant in all experiments (25 째C). Results for the best aeration level and strategy are commented below. DO concentration was easy to control in all experiments, increasing up to the desired value in a short period of time and reaching in a few minutes 0 mg/L in non aerated periods.As it was expected, Redox potential increased in aeration periods and decreased with the decreasing of DO concentration (Fig 52). As it was expected, Redox potential increased in aeration periods and decreased with the decreasing of DO concentration (Fig. 53). A linearly drop of conductivity is noticed with the progress of the reaction and pH tends to decrease, being this fall higher during anaerobic stages (Fig 54). More detailed data of physical parameters is shown in Appendix III.

57

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Fig. 52. DO profile during batch experiment no 12.

Fig. 53. Redox potential variation during batch experiment no 12.

Fig. 54. pH and conductivity variation during batch experiment no 12.

6.3. Conclusions Considering all the results from batch tests experiments with intermittent aeration, it may be concluded that:

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Evaluation of Deammonification process performance for supernatant treatment

• Oxygen is the main limiting factor. Dissolved oxygen level influences strongly the nitrogen removal efficiency in one-stage Deammonification process. • No aeration/aeration ratio and DO concentration influence nitrogen removal efficiency. • The best results were obtained with a no aeration/aeration ratio equal to 1/3 and for a dissolved oxygen concentration of 4 mg/L. • The production of nitrite during the partial nitritation seems to be the rate-limiting step for the Anammox reaction. • The change from aerobic to anaerobic conditions at the right time brings a reduction in costs and increase efficiency of the process. • It was proved that the better aeration strategy for the continuous system studied in lab-scale Deammonification reactors was different than the optimal aeration strategy found in batch tests experiments.

7. P ILOT PLANT D EA MMONIFICATION REACTOR After more than two months working with the Deammonification process in laboratory scale reactor, the next step was scaling-up this process to the pilot plant scale and starting a new reactor. Scaling-up of a process is essential to get practical knowledge and recognize operational problems in small-scale before a successful full-scale implementation.

7.1. Materials and methods In January 2010, a new Deammonification reactor started running in HSRS pilot plant. Initially, it consisted of two reactors with a volume of 200 L each and a settling tank after the reactors (Fig 55). However, only one of them was operated during the studied period. The reactor was filled up to 40 % of its volume with Kaldnes carriers, which were brought from Himmerfjärden WWTP. The reactor was continuously fed with supernatant from Bromma WWTP (Table 35). This supernatant had a high ammonium concentration around 1000 mg NH4+-N/L, high alkalinity and low organic matter content. Nitrite and nitrate concentration was almost 0 mg/L. Bromma supernatant characteristics were appropriate for carrying out the Deammonification process. Ammonium concentration in the inflow was fixed around 1000 mg/L using directly the fresh supernatant without dilution. Besides, the low content of biodegradable organic carbon in the feeding media avoided an over- growth of the heterotrophic bacteria. Continuous aeration was supplied from the bottom of the reactor to keep the DO level around 2 mg/L. The system was equipped with a vertical stirrer to provide suitable mixing and avoid sedimentation of biomass carriers. Mixing could be adjusted by controlling the speed of the stirrer. The influence of this parameter has been studied by (Arrojo et al., 2006) who reported that Anammox bacteria could support the high stress supplied by mechanical stirring up to 180 rpm but a decrease in the stability of Anammox granules was observed when speed was increased to 250 rpm. Also, a heater was used to keep a temperature inside the reactor around 25 °C. HRT was 2 days with a flow of 100 L/d until the 48th day of operation. During this period, influent nitrogen load to the reactor was 2.57 g N/m2 d on average. To determine the influence of nitrogen load increase on the process performance, the nitrogen load was increased to 3.81 g N/m2 d on average, which resulted in a HRT of 1.4 days. Operational parameters of the reactor are summarized in table 36. 59

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Table 35. Characteristics of supernatant from Bromma WWTP. Supernatant from Bromma

Unit

26/01/2009

18/03/2009

NH4+-N

mg/L

1040

1140

NO2--N

mg/L

1.59

0.76

NO3--N

mg/L

3.44

0.76

mmol/L

79.7

62.2

-

8.29

8.21

Conductivity

mS/cm

8.93

9.62

COD

mg O2/L

642

772

Alkalinity pH

Table 36. Operational parameters of Pilot Plant Deammonification reactor. Parameter

Unit

Value

Hydraulic retention time (HRT)

days

2 - 1.4

Reactor volume Flow Reactor filling with Kaldness rings

L

200

L/day

100 - 144

%

40

Measurements and analyses Process performance was followed up by physical measurements and chemical analyses. In this period, there were on-line devices in pilot plant (Fig. 56). In this way, physical parameters (pH, Temperature, DO, conductivity and Redox potential) were monitored easily every day. The equipment employed was the following: •

Redox, DO & pH - On-line equipment BB2 from Cerlic Company

•

Conductivity - Dr Lange Analon Cond 10

• Temperature - Jumo dTron 316 The sensors of these instruments were situated in the inflow pipe and inside the reactor to allow a continuous measurement of each parameter. Due to the complete mixing inside the reactor, values taken inside the reactor were assumed to be the same as in the outflow. Flow was checked daily to avoid strong fluctuations in the load into the system.

Fig. 55. Pilot plant Deammonification reactor.

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Evaluation of Deammonification process performance for supernatant treatment

Fig. 56. On-line equipment for measuring physical parameters in Pilot plant Deammonification reactor. Twice a week, samples were taken from the inflow tank and from the settling tank situated after the reactor. Chemical parameters were analyzed to follow the efficiency of the process: COD, ammonium, nitrite, nitrate and alkalinity. As in the previous experiments, Dr. Lange Tests were used for these analyses. Activity tests were performed once a week and the biomass developed on Kaldnes carriers (TSS and VSS) was also determined. Moreover, biofilm thickness was observed. SS in influent, effluent and activated sludge were also measured.

7.2. Results and discussion 7.2.1. Physical Parameters DO Dissolved oxygen was checked daily to assure a continuous aeration of 2 mg O2/L inside the reactor. The oxygen level was controlled with a rotameter connected to the supply pipe, and adjusted when it was required. After 30 days of operation, a decrease of pH in the outflow was observed, so it was decided to reduce the oxygen level to 1-1.5 mg/L (Fig 57) to limit the nitrification step, which resulted in an increase in the pH until stable values. By the end of the research period, DO concentration was increased again to 3 mg O2/L to evaluate the effect of an increase in the DO level. During the analyzed period, the control of DO level was easier than in lab-scale pilot plant. This may be due to the better quality of the oxygen pump compared to laboratory one and the well mixing of the bulk liquid. The DO concentration increased from the day 53, reaching a maximum peak of 3.8 mg/L (Fig 37). The DO increased but the efficiency remained constant. This can be due to the increase of the nitrogen load from 2.57 g N/m2 d to 3.81 g N/m2 d on average in the same period. pH During the period of study, pH of inflow was stable on the average of 8.0±0.3 and it was not required to adjust pH value adding chemical substances (Fig. 58). The pH of effluent was more unstable, with an average equal to 6.9±0.5, with a minimum of 5.6 (Table 38). A low pH value causes the production of nitrous acid, which must be avoided. For this reason when the pH in the effluent started to decrease, 61

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Table 37. DO variations of Deammonification reactor during the research period. Parameter

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Dissolved oxygen

mg O2/L

2.2

1.1

3.8

0.7

47

Table 38. pH variations of Deammonification reactor during the research period. pH

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Inflow

-

8.0

7.5

8.4

0.3

37

Outflow

-

6.9

5.6

8.0

0.5

47

t

Fig. 57. DO profile in Deammonification reactor during the operational period.

Fig. 58. Variation of pH in Deammonification reactor during the operational period. the level of oxygen was reduced to adjust the pH level and limit the nitritation step. More detailed data are shown in Appendix IV Conductivity As it was mentioned before, Deammonification process leads to a decrease in conductivity values due to the removal of two ions present in supernatant: ammonium and hydrogen (Fig 59). During the period of study, conductivity in the influent was very stable on the average of 9.55±0.15 mS/cm. Outflow profile experienced more ups and downs with an average of 1.63±0.54 mS/cm. connected with

62

Evaluation of Deammonification process performance for supernatant treatment

the changes on the nitrogen removal (Table 39).Detailed values are presented in Appendix IV. Temperature Temperature was an easy parameter to control in pilot plant Deammonification reactor as a result of the good mixing of the reaction liquid. The average value was almost 25 째C, being the last obtained values closer to the average than the earlier ones (Table 40 and Fig. 60). More details are shown in Appendix IV. Redox Potential Redox potential was also measured on-line for inflow and outflow of the pilot plant Deammonification reactor. ORP in influent was lower than in effluent due to the oxidizing ability of the solution (Fig 61). In both cases this parameter had fluctuations during the whole period (Table 41). More information is presented in Appendix IV.

Table 39. Conductivity variations of Deammonification reactor during the research period. Conductivity

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Inflow

mS/cm

9.55

9.22

9.87

0.15

47

Outflow

mS/cm

1.63

0.96

3.03

0.4

47

Table 40. Temperature variations of Deammonification reactor during the research period. Parameter

Unit

Average

Temperature

째C

24.8

Min. 24.0

Max.

St. Dev.

Number of samples

25.5

0.4

47

Table 41. Redox potential variations of Deammonification reactor during the research period. Redox Potential Inflow Outflow

Unit mV

St. Dev.

Number of samples

Average

Min.

Max.

-480

-539

-406

31

47

85

-11

237

60

47

Fig. 59. Variation of conductivity in Deammonification reactor during the operational period. 63

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Fig. 60. Temperature profile in Deammonification reactor during the operational period.

Fig. 61. Variation of redox potential in Deammonification reactor during the operational period. 7.2.2. Chemical Analyses NH4+-N concentration Ammonium concentration was measured in inflow and outflow of the reactor (Fig. 62). No other forms of inorganic nitrogen were analyzed in the influent because in the initial analysis of supernatant, nitrite and nitrate concentrations were almost zero. Ammonium concentration was kept stable in the influent with an average of 1021 mg/L while NH4+-N concentration in effluent decreased until 60.2 mg/L on average (Table 42). More details are shown in Appendix IV. NO2--N concentration Nitrite concentration in outflow remained quite stable until a drop caused by the reduction in DO concentration to the range 1-1.5 mg/L, which led to a slowdown in the nitritation process (Fig. 63). From the day 40th day, nitrite concentration was going up to 10 mg/L due to the increase of DO level (Fig. 57). High nitrite concentration in outflow must be avoided because it reflects that Anammox process was not performed efficiently. Nitrite concentration values are gathered in table 43. Detailed values are listed in Appendix IV.

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Evaluation of Deammonification process performance for supernatant treatment

Table 42. Ammonium concentration in Deammonification reactor during the research period. [NH4+-N] Inflow Outflow

Unit mg/L

Average

Min.

Max.

St. Dev.

Number of samples

1021

904

1110

53.8

9

60.2

20.6

163

40.2

13

Table 43. Nitrite concentration in Deammonification reactor during the research period. [NO2--N]

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Outflow

mg/L

7.01

4.34

10.41

1.89

13

Fig. 62. Ammonium profile in Deammonification reactor.

Fig. 63. Nitrite profile in Deammonification reactor. NO3--N concentration Nitrate was the main compound in the outflow from the reactor, being the nitrate production around 15 % (Fig 64). This value is higher than the stoichiometric one, 11 %. This difference between the theoretical and the experimental value could be due to the favorable conditions for the growth of nitrite Nitrite Oxidize Bacteria (NOB) in the outer layer of the biofilm, this is, the presence of oxygen and nitrite. 65

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Nitrate concentration during the operational period was on average 163.1Âą34.6 mg/L (Table 44) with a similar variation trend compared to nitrite profile (Fig. 63 and 65). This makes sense since if more nitrite is produced, more amounts are oxidized to nitrate. Detailed values are shown in Appendix IV. Alkalinity Alkalinity was measured in the influent and effluent of the Deammonification reactor. The values in inflow and outflow were rather stable but by the end of the period, it was observed a fluctuation both in inflow and outflow but following the same trend (Fig 66). Alkalinity decreased around a 97 % on average, but no lack of this parameter was noticed (Table 45). Detailed values are shown in Appendix IV

Table 44. Nitrate concentration in Deammonification reactor during the research period. [NO3--N]

Unit

Average

Min.

Max.

St. Dev.

Number of samples

Outflow

mg/L

163.1

122.2

235.0

34.6

13

Fig. 64 Evolution of nitrate Deammonification reactor.

production

in

Fig. 65. Nitrate profile in Deammonification reactor.

66

%

in

Evaluation of Deammonification process performance for supernatant treatment

Table 45. Alkalinity values in Deammonification reactor during the research period. Alkalinity Inflow Outflow

Unit

Average

mmol/L

Min.

Max.

St. Dev.

Number of samples

82.9

68

112

15.3

9

2.81

1.18

7.27

2.08

12

Fig. 66. Alkalinity profile in Deammonification reactor. COD During this period, the Chemical Oxygen Demand (COD) measurement was added to general chemical analysis to determine the amount of organic compounds present both in influent and effluent. In inflow, the organic material was higher but the profile was more unstable with a COD of 1060±264 mg O2/L on average. The COD in effluent suffered less fluctuation, being 311±49 mg O2/L on average (Table 46). The drop in the COD concentration between inflow and outflow (Fig 67) could be associated with minor nitrogen elimination due to heterotrophic denitrifying bacteria. Detailed values are shown in Appendix IV. To get an idea of the amount of organic material that remained in the filter as SS, samples of inflow of different days were analyzed unfiltered and after filtration with different pore size filters (Fig. 68). The results show that organic compounds present in inflow with sizes between 0.45 and 1.6 µm are in quantity as much as organic matter bigger than 1.6 µm.

Table 46. COD concentration in Deammonification reactor during the research period. Average

Min.

Max.

St. Dev.

Number of samples

Inflow (0.45 µm)

1060

637

1410

264

9

Inflow (1.6 µm)

1168

880

1320

198

5

1361

110 0

1610

216

5

311

180

380

49

12

COD

Inflow (Unfiltrated)

Unit

mg O2/L

Outflow (0.45 µm)

67

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Fig. 67. COD profile in Deammonification reactor.

Fig. 68. COD variations using different pore size filters.

7.2.3. Biomass measurements The determination of the biomass attached to Kaldnes rings was calculated using the procedure described in Standard Methods, 1999 (see chapter 4.4) (Table 47). VSS represent the amount of biomass attached to carriers; in this case, it refers to nitrifying, Anammox and also denitrifying bacteria. Comparing the initial and final values for the VSS from the biomass, the increase means a rise in the bacteria population (Fig 69). However, fluctuations in this value can be caused by the detachment or wash-out of any of the initial bacteria of the system. That is why it was considered important to determine the concentration of suspended solids in the supernatant before and after the reactor. 7.2.4. Suspended Solids (SS) in supernatant The concentration of SS in supernatant is an important parameter in the control of the Deammonification process. High concentration of solids has impact on process performance. They are usually controlled in WWTPs to avoid clogging of the pipes and ensure the compliance with discharge regulations.

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Evaluation of Deammonification process performance for supernatant treatment

Table 47. Biomass developed on Kaldnes carriers. Parameter TSS VSS

Unit g/L

Average

Min.

Max.

St. Dev.

Number of samples

14.44

12.80

17.17

1.75

8

13.14

11.69

15.75

1.59

8

Table 48. Analyses of Total Suspended Solids (TSS) in inflow, outflow and activated sludge. TSS

Unit

Inflow Activated sludge

g/L

Outflow

Average

Min.

Max.

St. Dev.

Number of samples

0.141

0.107

0.205

0.042

5

0.434

0.310

0.701

0.159

5

0.406

0.077

0.710

0.281

5

Table 49. Analyses of Volatile Suspended Solids (VSS) in inflow, outflow and activated sludge. VSS

Unit

Inflow Activated sludge

g/L

Outflow

Average

Min.

Max.

St. Dev.

Number of samples

0.122

0.077

0.165

0.035

5

0.369

0.275

0.559

0.115

5

0.330

0.065

0.516

0.216

5

Fig. 69. TSS, VSS from biomass of Deammonification reactor. For this reason, the concentration of suspended solids was also analyzed in the inflow, outflow and activated sludge inside the reactor once a week during the whole evaluated period. The average value in the influent was 0.141 g TSS/L and 0.122 g VSS/L whereas for the outflow the average values were higher (0.406 g TSS/L and 0.330 g VSS/L). Values for the activated sludge were 0.434 g TSS/L and 0.369 g VSS/L on average (Table 48 and 49). Solids concentration in the influent was rather low and it was progressive increased inside the reactor and in the outflow (Fig. 70 and 71), probably due to the biofilm detachment and the growth of the biomass.

69

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Fig. 70. TSS analyses

Fig. 71. VSS analyses. The fact that there were not important changes on efficiency connected with the concentration of biomass in the rings because the increase of bacteria population is balanced with the evident biofilm detachment from the rings. 7.2.5. Bacterial activity measurements Specific Anammox Activity SAA tests were carried out according to Dapena-Mora et al. (2007). Following this methodology, the activity measured is a potential activity referring to the maximum activity of Anammox bacteria without substrate limitations for the range of ammonium and nitrite. During the studies performed in the pilot plant reactor, tests were done at the optimal temperature of 35 °C but they were also carried out at the operational temperature of 25 °C to check the temperature influence in the bacteria activity. As it was expected, high Anammox activity was measured at 35 °C with an average of 2.931 g N/m2 d and a maximum of 3.176 g N/m2 d. Lower temperature led to an activity of 2.079 g N/m2 d. with a maximum of 2.565 g N/m2 d (Table 50). It has been reported that between 20 °C and 37 °C the activity of Anammox bacteria follows the Arrhenius law increasing with the increase of the temperature (Dosta et al., 2007). Activity decreased 30 % decreasing 10 °C the temperature (Fig 72).

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Evaluation of Deammonification process performance for supernatant treatment

Table 50. SAA in g N/m2 d measured at 35˚C and 25˚C. Parameter SAA (35˚C) SAA (25˚C)

Unit

Average

Min.

Max.

St. Dev.

Number of samples

2.961

2.831

3.176

0.133

6

2.079

1.770

2.565

0.273

6

g N/m2·d

Table 51. SAA in g N/gVSS d measured at 35˚C and 25˚C. Paramenter SAA (35˚C) SAA (25˚C)

Unit g N/gVSS·d

Average

Min.

Max.

St. Dev.

Number of samples

0.072

0.060

0.079

0.007

6

0.054

0.047

0.069

0.008

6

Fig. 72. SAA referred to the biofilm area.

Fig. 73. SAA referred to the amount of VSS. Previous results are referred to the biofilm area but it is also useful to calculate Anammox activity per grams of VSS. (Table 51 and Fig. 73). Deammonification process activity Apart from the potential Anammox activity, it is also useful to estimate the real activity of the bacteria under the specific operational conditions (Table 52). 71

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As it was expected, potential SAA was always higher than the Deammonification activity (Fig 74). In this way, comparing both amounts it is possible to evaluate the overall activity of the bacteria and the performance of our system. To analyze the effect of the nitrogen load increase in the Deammonification process activity, the figure 75 is presented. Parallel to the progressive increase of the nitrogen load from 2.5 to 4 g N/m2 d, the Deammonification process activity also increased from 2.28 to 3.36 g N/m2 d. This trend means that the system had some capacity left before increasing the nitrogen load value. Moreover, the biomass attached to the rings was growing during this period (see Fig. 69). Szatkkowska et al. (2007) studied also the effect of a nitrogen load increase and they reported that the average nitrogen removal rate was insignificantly higher evidencing there was no capacity left in that system.

Table 52. Deammonification activity during the operational period. Days

Deammonification activity g N/m2·d)

25

2.198

30

1.806

35

1.916

40

2.275

50

2.545

60

2.756

Fig. 74. Comparison between SAA and Deammonification activity.

Fig. 75. Comparison between nitrogen removal rate and nitrogen load in the influent. 72

Evaluation of Deammonification process performance for supernatant treatment

Table 53. Total nitrogen and ammonium removal efficiency of Pilot Plant Deammonification reactor. Unit Total nitrogen removal efficiency

Average

Min.

Max.

St. Dev.

Number of samples

76.5

67.8

84.5

6.5

9

93.6

84.3

97.2

4.2

9

%

Ammonium removal efficiency

Fig. 76. Total inorganic nitrogen and ammonium removal efficiency of the pilot plant reactor. 7.2.6. Removal efficiency The Deammonification reactor was operating with a high efficiency during the analyzed period. The ammonium removal was 93.6±4.22 % on average, with a maximum in 97.2 %, whereas the total inorganic nitrogen removal during the research period was 76.5±6.5 % (Table 53), decreasing until the minimum registered value, 67.8 %, around day 50. This could be due to an increase in the nitrogen load in influent or a decrease in oxygen supply to 1-1.5 mg O2/L. Then, the efficiency started to increase again, and after two months of operation, the total nitrogen removal was almost 84 % (Fig 76). Detailed values are listed in Appendix IV.

7.3. Conclusions • Supernatant delivered from Bromma WWTP was characterized by high alkalinity and ammonium concentration and low organic matter content. • An increase in the influent nitrogen load resulted in an increase in the nitrogen removal rate after an adaptation period of the bacteria. • The COD removal from 1060 mg O2/L to 311 mg O2/L on average due to nitrogen elimination suggested that heterotrophic denitrifying bacteria were also responsible for the overall nitrogen removal together with the Anammox process. • On-line control of physical parameters (especially DO) provide reliable and quickly data about the influence of changing operational parameters on the process performance.

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• The reactor was operating with high nitrogen removal efficiency with an average of 76.5%. Maximum nitrogen removal efficiency was 84.5%. • Specific Anammox activity is influenced by temperature following the Arrhenius law. SAA decreased 30% decreasing 10°C the temperature. • Fluctuations in the biofilm thickness evidenced a progressive growth in the bacteria population together with some wash-out of any of the initial bacteria of the system due to frictions between the carriers. • Detachment of the biomass from the carriers resulted in a progressive increase in the suspended solids concentration in the reactor. • Redox potential was the most changeable parameter and its fluctuations depend on the DO level. • Decrease in pH in the effluent due to the alkalinity consumption during the nitritation step could be adjusted by decreasing the DO level inside the reactor to prevent further oxidation of nitrites to nitrates.

8. G ENERAL CONCLUSIONS The application of Anammox reaction for one-stage Deammonification process was investigated in this thesis. Deammonification process was applied in laboratory-scale in two different system configurations as well as in bigger pilot plant scale. Additionally, discontinuous experiments were performed to find out the possible optimal strategy of aeration. Extended description of specific conclusions can be found in the discussion of different chapters. Summarizing the six months of experimental work presented in this thesis, it can be concluded that: • Partial nitritation/Anammox process is a sustainable alternative that can be successfully applied for nitrogen removal from ammoniumrich streams of industrial and municipal wastewaters. • The co-existence between nitrifiers and Anammox bacteria in the biofilm makes able to perform two processes simultaneously in a single reactor. • Suitable oxygen conditions together with adequate influent nitrogen load and proper hydraulic retention time is indispensable for high nitrogen removal rates. • Nitrite production and dissolved oxygen level in the reaction liquid seem to be the limiting factors for the Anammox reaction in a onestage single reactor. • Conductivity measurements are a simple and effective tool for process monitoring. • Influence of temperature on the removal rates is a key factor. Partial nitritation/Anammox process can be successfully applied at lower temperatures than the optimum value decreasing operational costs. • A separate treatment of the supernatant with partial nitritation/Anammox process enables a reduction of the nitrogen load in the effluent of the WWTP’s. • Changes on physical parameters and nitrogen forms profiles are a tool to follow up and monitor the system performance.

74

Evaluation of Deammonification process performance for supernatant treatment

• SAA tests based on the measurement of the nitrogen gas pressure enable to know the decrease or increase of bacteria activity. In case of lost of bacteria activity, time is needed for the process recovery. • Temperature was the most stable parameter while dissolved oxygen level and Redox potential were the most unstable parameters with big fluctuations over the research period. • Experimental results from laboratory scale and pilot plant scale are guidelines for future design of full-scale Deammonification systems.

9. R ECOMENDATIONS FOR FUTURE STUDIES The experimental work done during this thesis, together with a wide literature review have proved that the partial nitritation/Anammox process can be successfully applied as an alternative for nitrogen removal from wastewater. However, there are still several aspects that have to be investigated by future researchers to make possible a full-scale implementation of this process such as: • Identification of toxic substances present in wastewater to avoid the possible process inhibition. • Prevention the algae growth by protecting the system from the light. • Speed-up the process start-up using different strategies such as the use of catalysts for the reaction initiation. • Efficient retention of the biomass to avoid biofilm detachment is required due to the slow growth rate of the Anammox bacteria. Biofilm thickness should be examined. • Influence of biofilm thickness on the Deammonification efficiency. • Further investigations about the application of the Redox potential for monitoring the process performance. • Studies of the survival ability of Anammox bacteria under different conditions. • Further investigations about intermittent aeration strategy in one single partial nitritation/Anammox reactor. • Effect of the mechanical stress and agitation speed on the Anammox culture.

75

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

10. R EF ERENCES Ahn, Y. H., Hwang, I. S. & Min, K. S. 2004. Anammox and partial denitritation in anaerobic nitrogen removal from piggery waste. Water Science and Technology, 49 (5-6): 145-153. Anthonisen, A. C., Loehr, R. C., Prakasam, T. B. S. & Srinath E. G. 1976. Inhibition of nitrifi-cation by ammonia and nitrous acid. Journal WPCF, 48 (5): 835-852. Arrojo, B., Mosquera-Corral, A., Campos, J.L. & Méndez, R. 2006. Effects of mechanical stress on Anammox granules in a sequencing batch reactor (SBR). Journal of Biotechnology, 123: 453-463. Buddhavarapu, S. & Inniss, E. C. 2006 Activated sludge characterization by ORP profiles. Department of Civil and Environmental Engineering. University of Texas at San Antonio. Proceedings of Texas Water 2006 conference: 124-130. Cema, G. 2009. Comparative study on different Anammox systems. Phd Thesis, Land and Water Resources Engineering Department, KTH University, Stockholm, Sweden. 72 p. Cema, G., Plaza, E., Trela, J. & Surmacz-Górska, J. 2008. Dissolved oxygen as a factor influencing nitrogen removal rates in a one-stage system with partial nitritation and Anammox process. Proceedings of the IWA Biofilm Technologies Conference 8-10 January, Singapore. Submitted for publication in Water Science and Technology. Cema, G., Wiszniowski, J., Zabczynski,S., Zabłocka-Godlewska, E., Raszka, A. & Surmacz-Górska, J. 2007 Biological nitrogen removal from landfill leachate by deammonification assisted by heterotrophic denitrification in a rotating biological contactor (RBC). Water Science and Technology, 55 (8-9): 35-42. Cervantes-Carrillo, F., Pérez, J. & Gómez, J. 2000. Avances en la eliminación Biológica del Nitrógeno de las Aguas Residuales. Revista Latinoamericana de Microbiología, 42: 73-82. In Spanish. Dalsgaard T., Thamdrup B. & Canfield D. E. 2005. Anaerobic ammonium oxidation (anammox) in the marine environment. Research in Microbiology, 156 (4): 457-464. Dapena-Mora, A. Campos, J. L., Mosquera-Corral, A., Jetten, M. S. M. & Méndez, R. 2004. Stability of the ANAMMOX process in a gaslift reactor and a SBR. Journal of Biotechnology, 110: 159-170. Dapena-Mora, A., Campos, J.L., Mosquera-Corral, A. & Méndez, R. 2006. Anammox process for nitrogen removal from anaerobically digested fish canning effluents. Water Science and Technology, 53 (12): 265274. Dapena-Mora, A., Fernández, I., Campos, J.L., Mosquera-Corral, A., Méndez, R. & Jetten, M. S. M. 2007. Evaluation of activity and inhibition effects on Anammox process by batch tests based on the nitrogen gas production. Enzyme and Microbial Technology, 40: 859-865. Dosta, J., Fernández, I., Vazquez-Padín, J.R., Mosquera-Corral, A., Campos, J.L., Mata-Álvarez, J. & Méndez, R. 2008. Short- and longterm effects of temperature on the Anammox process. Journal of Hazardous Materials, 154: 688-693. Egli, K., Fanger, U., Alvarez, P. J. J., Siegrist, H., Van der Meer, J.R. & Zehnder, A.J.B. 2001. Enrichment and characterization of anammox

76

Evaluation of Deammonification process performance for supernatant treatment

bacterium from a rotating biological contacter treating ammoniumrich leachate. Archives of Microbiology, 175: 198-207. Fernández, I., Figueroa, M., Vázquez, J. R., Mosquera, A., Campos, J. L. & Méndez, R. J. 2007. Proceso Anammox: Un cortocircuito en el Ciclo del Nitrógeno para la depuración de aguas residuales. Revista técnica de Medio Ambiente RETEMA 1616: 34-47. In Spanish. Fux, C., Boehler, M., Huber, P., Brunner, I. & Siegrist, H. 2002. Biological treatment of ammonium-rich wastewater by partial nitritation and subsequent anaerobic ammonium oxidation (anammox) in a pilot plant. Journal of Biotechnology, 99: 295-306. Gut, L. 2006. Assessment of a partial nitritation/Anammox system for nitrogen removal. Trita-LWR LIC: 2034, licentiate thesis, 57 p. Güven, D., Dapena, A., Kartal, B., Schmid, M. C., Maas B., van de PasSchoonen, K., Sozen, S., Méndez, R., Op den Camp, H. J. M., Jetten, M. S. M., Strous, M. & Schmidt, I. 2005. Propionate oxidation by and methanol inhibition of anaerobic ammonium-oxidizing bacteria. Applied and Environmental Microbiology, 71 (2): 1066-1071. Hao, J.O. & Kim, H. 2000. pH and oxidation reduction potential (ORP) strategy for optimization of nutrient removal in an alternatingaerobic–anoxic system. Water Environ. Res. 73 (1): 95-102. HELCOM Stakeholder Conference on the Baltic Sea Action Plan. Helsinki, Finland, 7 March 2006. Hellinga, C., Schellen. A. A. J. C., Mulder, J. W., van Loosdrecht, M. C. M. & Heijnen, J. J. 1998. The SHARON process: an innovative method for nitrogen removal from ammonium-rich wastewater. Water Science Technology, 37: 135–142. Helmer, C. & Kunst, S. 1998. Simultaneous nitrification/denitrification in anaerobic biofilm system. Water Science and Technology, 37 (4-5): 183-187. Holman, J. B. & Wareham, D. G. 2003. Oxidation-Reduction Potential as a Monitoring Tool in a Low Dissolved Oxygen Wastewater Treatment Process. Journal of Environmental Engineering, 129 (1): 52-58. Hultman, B. & Plaza, E. 2009. Wastewater treatment -new challenges. Conference: Research and application of new technologies in wastewater treatment in Ukraine, Sweden and Poland. September, Stockholm, Sweden. Jetten, M. S. M., Cirpus, I., Kartal, B., van Niftrik L., van de PasSchoonen K. T., Sliekers, O., Haaijer, S., van der Star, W., Schmid, M., van de Vossenberg, J., Schmidt, I., Harhangi, H., van Loosdrecht, M., Kuenen, J.G., Op den Camp, H. & Strous M. 2005. 1994-2004: 10 Years of research on the anaerobic oxidation of ammonium. Biochemical Society Transactions, 33(1): 119-123. Jetten, M. S. M., Wagner, M., Fuerst, J., Van Loosdrecht, M., Kuenen, G. & Strous, M. 2001. Microbiology and application of the anaerobic ammonium oxidation (anammox) process. Environmental Biotechnology, 12: 283-288. Jung, J. Y., Kang, S. H., Chung, Y. C. & Ahn, D. H. 2007. Factors affecting the activity of anammox bacteria during start up in the continuous culture reactor. Water Science & Technology, 55 (1-2): 459-468. Kangro, K., Olli, K., Tamminen, T. & Lignell, R. 2007. Species-specific responses of a cyanobacteriadominated phytoplankton community to

77

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

artificial nutrient limitation in the Baltic Sea. Marine Ecology Progress Series, 336: 15-27. Khalili, M. 2007. Salt, water and nutrient fluxes to Himmerfjärden bay. Department of Earth Sciences, Uppsala University, Villavägen 16, SE752 36 Uppsala. ISSN 1401-5765. Lekang, O.-I. & Kleppe H. 2000. Efficiency of nitrification in trickling filters using different filter media. Aquacultural Engineering, 21: 181-199. Malovanyy, A. 2009. Monitoring and application of Anammox process in one stage deammonification system.TRITA-LWR MASTER Malovanyy, A., Plaza, E. & Trela, J. 2009. Evaluation of the factors influencing the specific Anammox activity (SAA) using surface modeling. Department of Land and Water Resources Engineering. Royal Institute of Technology (KTH). Research and application of new technologies in wastewater treatment in Ukraine, Sweden and Poland. (Polish-UkranianSwedish seminar). Mota, C., Head, M. A., Ridenoure, J. A., Cheng, J. J. & de los Reyes, F. L. 2005. Effects of Aeration Cycles on Nitrifying Bacterial Populations and Nitrogen Removal in Intermittently Aerated Reactors. Applied and Environmental Microbiology, December: 8565–8572. Mulder, A., Van de Graaf, A. A., Robertson, L. A. & Kuenen, J. G. 1995. Anaerobic ammonium oxidation discovered in denitrifying fluidized bed reactor. FEMS Microbiology Ecology, 16: 177-184. Paques. 2007. Unique combination of biological technologies at tannery (www.paques.nl). Ridenoure, J. 2004. Optimization of nitrogen removal from anaerobically pretreated swine wastewater (APTSW) in intermittent aeration reactors. Master of Science Thesis, North Carolina State University. 150 pp. Rönnberg, C. & Bonsdorff, E. 2004. Baltic Sea eutrophication: areaspecific ecological consequences. Hydrobiologia, 514: 1-3. Siegrist, H. 1996. Nitrogen removal from digester supernatant –comparison of chemical and biological methods. Water Science and Technology, 34(1-2): 399-406. Siegrist, H., Reithaar, S., Koch, G. & Lais, P. 1998. Nitrogen loss in nitrifying rotating contactor treating ammonium-rich wastewater without organic carbon. Water Science and Technology, 38 (8-9): 241-248. Standard Methods for the Examination of Water and Wastewater. 1999. American Public Health Association, American Water Works Association, Water Environment Federation. Strous M., Van Gerven E., Kuenen J. G. & Jetten M. 1997b. Effects of aerobic and microaerobic conditions on anaerobic ammoniumoxidizing (Anammox) sludge. Applied and Environmental Microbiology, 63 (6): 2446-2448. Strous M., Van Gerven E., Zheng P., Gijs Kuenen J. & Jetten M.S.M. 1997a. Ammonium removal from concentrated waste streams with the anaerobic ammonium oxidation (Anammox) process in different reactor configuration. Water Resources, 31 (8): 1955-1962. Strous, M. 2000. Microbiology of anaerobic ammonium oxidation. Delft University of Technology. Doctoral Thesis. Szatkowska, B. 2004. Treatment of ammonium-rich wastewater by partial nitritation/Anammox in a biofilm system. Licenciate Thesis, Royal Institute of Technology, Stockholm, Sweden. TRITA-LWR.LIC 2023. 78

Evaluation of Deammonification process performance for supernatant treatment

Szatkowska B. & Plaza E. 2006. Temperature as a factor influencing the Anammox process performance. Water and Environmental Management Series, Young Researchers 2006: 51-58. Szatkowska, B. 2007. Performance and control of Biofilm Systems with Partial Nitritation and Anammox for Supernatant Treatment. TRITA-LWR PhD Thesis 1035, 63 p. Szatkowska, B., Cema, G., Plaza, E., Trela, J. & Hultman, B. 2007. A one stage system with partial nitritation and Anammox processes in the moving-bed biofilm reactor. Water Science and Technology, 55: 19-26. Tanwar, P., Nandy, T., Ukey, P. & Manekar, P. 2008. Correlating on-line monitoring parameters, pH, DO and ORP with nutrient removal in an intermittent cyclic process bioreactor system. Bioresource Technology, 99: 7630-7635. Third, K. A., Paxman, J., Schmid, M., Strous, M., Jetten M. S. M. & Cord-Ruwisch, R. 2005. Enrichment of anammox from activated sludge and its application in the CANON process. Microbiology Ecology, 49 (2): 236-244. Trigo, C., Campos, J. L., Garrido, J. M. & Méndez, R. 2006. Start-up of the Anammox process in a membrane bioreactor. Journal of Biotechnology, 126: 475-487. Van de Graaf, A. A., Mulder, A., de Bruijn, P., Jetten M. S. M., Robertson, L. A. & Kuenen, J. G. 1995. Anaerobic oxidation of ammonium is a biologically mediated process. Applied and Environmental Microbiology, 61: 1246-1251. Van Dongen, L. G. J. M., Jetten, M. S. M. & Van Loosdrecht, M. C. M. 2001. The combined Sharon/Anammox Process, a sustainable method for N-removal from sludge water. STOWA Report, IWA Publishing, London, UK. Vázquez-Padín, J., Fernández, I., Figueroa, M., Mosquera-Corral, A., Campos, J. L. 2009. Applications of Anammox based processes to treat anaerobic digester supernatant at room temperature. Bioresource Technology, 100: 2988-2994. Villaverde, S. 2004. Recent developments on biological nutrient removal processes for wastewater treatment. Reviews in Environmental Sience and Bio/Technology, 3: 171-183. Zhang, L., Zheng, P., Tang, C-j., Jin, R-c. 2007. Anaerobic ammonium oxidation for treatment of ammonium-rich wastewaters. (www.eidenar.univalle.edu.co/revista/ejemplares/8/k.htm). Yang, J. 2009. Optimization of Canon process and start-up process. TRITALWR Degree Project 1651, 42 p. Other references: www.sjostadsverket.se www.anoxkaldnes.com

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Evaluation of Deammonification process performance for supernatant treatment

APPENDIX I. DATA OF MEASUREMENTS AND ANALYSES FROM LAB-SCALE DEAMMONIFICATION REACTORS (SERIAL SYSTEM) DURING OCTOBER 13ST 2009 – NOVEMBER 24TH 2009.

Table 1A.Data of physical parameters (Ph, conductivity, ORP, Do and temperature) in lab-scale Deammonification reactors during October 13th 2009 – November 24th 2009. INFLOW Days

HRT (Days)

2

R1

pH

Conductivity (mS/cm)

DO (mg/L)

2

8.08

3.9

4

2

8.28

5

2

8.11

R2

pH

Conductivity (mS/cm)

T (°C)

DO (mg/L)

3,51

7.96

3.7

17

3.51

3.97

7.65

3.45

17.2

3.74

2.9

7.8

3.64

OUTFLOW

pH

Conductivity (mS/cm)

T (°C)

pH

Conductivity (mS/cm)

3,8

7.61

3.62

19.3

7.94

2.98

3.48

7.82

3.27

19.9

7.86

2.87

2.5

7.79

3.35

7.79

2.95

8

2

8.33

3.65

2.85

8.11

3.48

18.1

3.05

7.71

3.26

16.2

7.66

2.59

10

2

8.2

3.61

3.6

6.78

3.61

18.8

3.51

6.96

3.16

20.6

7.27

3.05

12

2

8.02

3.97

3.13

6.11

3.7

18.3

3.43

5.32

3.22

20.2

5.29

3

15

2

7.9

3.86

3.06

6.12

3.51

18.6

3.03

5.52

3.26

18.7

5.37

3.25

16

2

7.74

3.76

3.95

5.43

3.66

19.1

3.37

5.17

3.52

19.3

6.22

3.36

17

2

7.79

3.94

3.65

5.9

3.55

3.02

5.69

3.23

6.12

3.22

18

2

7.85

4.02

2.71

6.38

3.62

16.9

3.41

5.62

3.6

17.1

5.47

3.15

19

2

7.91

3.99

3.27

6.6

3.57

15.9

3.14

5.95

3.19

15.5

5.93

3.05

22

2

7.95

4.04

3.98

6.37

3.44

17.8

3.21

5.9

3.1

17.8

6.49

3.09

24

2

7.77

3.68

2.23

6.7

3.54

18

3.02

5.87

3.51

17.5

5.95

3.35

25

2

7.82

3.75

2.87

6.68

3.38

2.6

6.3

3.12

6.12

2.98

26

2

7.56

3.63

3.95

6.81

3.43

17

1.75

6.41

2.89

16.7

6.7

2.84

29

2

7.67

3.52

3.78

5.91

3.32

17.5

3.43

4.93

3.21

17.2

5.32

2.9

31

2

7.62

3.6

3.71

6.12

3.5

17.5

4.54

4.46

2.9

19.4

4.5

2.9

36

2

7.82

4.18

3.26

5.15

3.58

18.9

3.8

4.51

3.2

20.4

4.64

3.08

37

2

7.89

3.89

3.9

6.3

3.3

3.32

5.45

3.17

5.15

3.27

38

2

7.92

3.75

3.4

6.86

3.55

3.69

5.3

3.34

5.32

3.14

39

2

7.77

4.04

2.8

6.36

3.86

44

2

7.69

3.98

3.06

6.67

3.2

18.3

I

3.21

5.24

3.3

3.63

5.42

3.11

20.6

5.47

3.05

5.38

3.12

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

Table 2A. Data of chemical parameters (NH4+, NO3-, NO2-, alkalinity) and efficiency in lab-scale Deammonification reactors during October 13th 2009 – November 24th 2009. INFLOW NH4+

OUTFLOW

(mg/L)

Alkalinity (mmol/L)

2

366

22.2

4

319

24.2

Days

5

EFFICIENCY

NH4+

NO3-

NO2-

(mg/L)

(mg/L)

(mg/L)

Alkalinity (mmol/L)

Total Nitrogen Removal (%)

Ammonium Removal (%)

1.34

0.28

53.2

4.2

82.90

99.58

8 10 12

484

14.5

355

0.11

48.2

4.68

16.69

26.65

497

7.88

350

0.49

38.2

4.71

21.79

29.58

480

11.1

349

0.3

37.8

3.9

19.42

27.29

411

0

24.7

2.9

17.32

22.01

15 16 17 18 19 22 24 25 26 29 31 36 37 38

527

6.78

39 44

II

Evaluation of Deammonification process performance for supernatant treatment

Table 3A. Data for determination of biomass attached to Kaldnes rings in lab-scale Deammonification Reactor 1 (R1) during October 13st 2009 – November 24st - 2009. BIOMASS Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

24

4

2.6126

2.6715

2.6198

13.98

12.28

38

4

1.0682

1.1266

1.0713

13.87

13.13

44

4

1.0656

1.1229

1.0679

13.61

13.06

Table 4A. Data for determination of biomass attached to Kaldnes rings in lab-scale Deammonification Reactor 2 during October 13st 2009 – November 24st 2009. BIOMASS Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

24

4

2.6126

2.6715

2.6198

13.98

12.28

38

4

1.0574

1.1107

1.0613

12.66

11.73

44

4

1.0696

1.1198

1.0705

11.92

11.71

III

Evaluation of Deammonification process performance for supernatant treatment

Table 5A. Data of pressure for calculation of SAA of biomass from lab-scale Deammonification reactors during October 13st 2009 – November 24st 2009. 11.04.2009 Time (min)

P (mV) R1

0

P(mV) R2

11.18.2009

11.24.2009

P (mV) R1

P(mV) R2

P (mV) R1

P(mV) R2

5

4.6

4.8

4.1

3.3

40

27.3

30.2

21.4

36.4

14.8

80

40.4

42.7

30.8

47.7

15.5

120

49.9

47.7

36.6

56.9

20.1

160

52.4

54.4

45

60.3

20.4

200

51.1

57.3

51.2

61.3

22

IV

Evaluation of Deammonification process performance for supernatant treatment

APPENDIX II. DATA OF MEASUREMENTS AND ANALYSES FROM THE LAB-SCALE DEAMMONIFICATION REACTORS (PARALLEL SYSTEM) DURING NOVEMBER 27ST 2009 – DECEMBER 21TH 2009.

Table 6A. Data of physical parameters (Ph, conductivity, ORP, DO and temperature) in lab-scale Deammonification reactors during November 27th 2009 – December 21th 2009. INFLOW

R1

R2

OUTFLOW R1

OUTFLOW R2

Days

HRT (Days)

Ph

Conductivity (mS/cm)

Redox (mV)

T (°C)

T (°C)

Ph

Conductivity (mS/cm)

Redox (mV)

Ph

Conductivity (mS/cm)

Redox

1

2

8.09

5.7

-50

29.2

29

7.8

1.65

38

8.28

3.9

64

4

2

8.37

5.4

-68

29.5

30.1

7.79

1.5

-34

8.06

2

51

5

2

7.95

6.55

-43.8

28

27.8

7.3

1.6

57

8.01

1.6

26.8

6

2

8.02

7.09

-55.25

27

27.8

7.1

1.67

65.4

7.51

1.58

61.3

7

2

8.09

6.89

-69.5

27

26.8

6.63

2.01

120.4

7.44

1.9

76.8

8

2

7.91

7.61

-58.4

26.9

26.9

6.31

2.29

118.1

7.25

2.1

74.5

11

2

8.11

6.86

-55.4

26.4

26.9

5.79

4.43

180.1

5.74

4.25

141.2

12

2

8.21

6.75

-29.9

27

27.3

6.94

3.81

105.8

7.03

3.22

71.6

13

2

8.2

6.92

-22.5

27.1

26.9

6.72

3.26

140.9

7.21

3.03

59.9

14

2

8.07

6.7

-103

27.3

26.7

7.09

2.7

47.9

6.89

2.3

-43.7

15

2

8.15

6.8

-68.5

27.5

27.4

6.94

2.3

79.4

7.03

2.1

28

18

2

8.17

6.5

-53.7

27.1

26.2

7.58

2.6

27.5

7.4

2.06

41.4

19

2

8.1

6.9

-43.1

27.2

26.5

7.2

2.2

89

7.21

1.9

38

20

2

8.24

5.96

-7.1

26.5

26.1

7.68

2.02

60.3

7.14

0.96

64.1

21

2

8.21

5.9

-286.5

25.5

26.4

7.61

1.77

78.3

7.55

0.88

-24.9

22

2

8.22

5.9

-52.3

25.9

26.2

7.57

1.56

29.3

7.41

1.06

29.8

25

2

8.23

5.7

-69.9

26

26.4

7.3

1.5

35.8

7.28

1.23

56.9

V

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

Table 7A. Data of chemical parameters (NH4+, NO3-, NO2-, alkalinity) and efficiency in lab-scale Deammonification reactors during November 27th 2009 – December 21th 2009. INFLOW

Days

NH4+ (mg/L)

1

877

Alkalinity (mmol/L)

OUTFLOW R1 NH4+ (mg/L)

5.92

4 5

850

6

850

NO3(mg/L)

52.6

NO2(mg/L)

3.23

OUTFLOW R2 Alkalinity (mmol/L)

5.76

NH4+ (mg/L)

NO3(mg/L)

NO2(mg/L)

460

2.2

2.15

96.8

4.38

4.87

EFFICIENCY R1 Alkalinity (mmol/L)

Nitrogen removal (%)

Ammonium removal (%)

Nitrogen removal (%)

Ammonium removal (%)

99.32 14.7

92.96

88.46

88.96

52.8

92.48

7 8

897

11

850

66.8

63.9

103

3.52

272

92.5

2.13

4.55

63.1

29.9

6.84

252

50.5

8.19

4.8

79.95

88.25

59.13

65.36

69.68

92.58 71.91

81.41

12 13

EFFICIENCY R2

865

67.6

158

108

3.1

0.969

176

40.6

6.63

9.34

68.71

74.52

79.29 90.10

14 15

835

55.5

85.6

104

3.48

1.6

70.7

52

6.87

4.19

77.68

85.02

18

829

57.5

79.4

82

5.64

5.66

36.6

54.5

10.3

4.1

80.00

87.86

90.49

91.83 95.62

19 20

830

21 22 25

820

52.8

81.10 155

2.35

3.7

19.1

64.3

7.7

VI

5.28

11.5

80.36

90.58

92.16

Evaluation of Deammonification process performance for supernatant treatment

Table 8A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (11.31.2009). 11.31.2009

R1

Time (min)

DO (mg/L)

R2 Redox (mV)

Time (min)

DO (mg/L)

0

0.33

0

0.09

1.25

0.93

1.25

0.33

2.5

1.49

2.5

1.04

3.75

1.81

3.75

1.41

5

2.37

5

1.79

6.25

2.43

6.25

2

7.5

2.52

7.5

2.21

8.75

2.59

8.75

2.35

10

2.71

10

2.52

11.25

2.73

11.25

2.6

12.5

2.79

12.5

2.68

13.75

2.79

13.75

2.71

15

2.79

15

2.75

16.25

2.83

16.25

2.77

17.5

2.85

17.5

2.79

18.75

2.85

18.75

2.8

20

2.88

20

2.8

21.25

2.92

21.25

2.85

22.5

2.94

22.5

2.8

23.75

2.95

23.75

2.89

25

2.97

25

2.8

26.25

3

26.25

2.43

27.5

2.99

27.5

1.98

28.75

2.97

28.75

1.37

30

2.26

30

0.89

31.25

1.76

31.25

0.47

32.5

1.36

32.5

0.33

33.75

0.93

33.75

0.18

32.5

0.64

32.5

0.11

33.75

0.47

33.75

0.07

35

0.35

35

0.05

36.25

0.27

36.25

0.05

37.5

0.2

37.5

0.04

38.75

0.14

38.75

0.03

40

0.13

40

0.03

41.25

0.1

41.25

0.03

42.5

0.16

42.5

0.03

43.75

0.02

43.75

0.02

45

0.02

45

VII

Redox(mV)

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

46.25

46.25

0.02

47.5

47.5

0.02

48.75

48.75

0.02

50

50

0.02

51.25

51.25

0.01

52.5

52.5

0.01

53.75

53.75

0.02

55

55

0.01

56.26

56.26

0.02

57.5

57.5

0.02

58.75

58.75

60

60

VIII

Evaluation of Deammonification process performance for supernatant treatment

Table 9. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.03.2009). 12.03.2009 Time (min)

R1 DO (mg/L)

R2

Redox (mV)

Time (min)

DO (mg/L)

Redox(mV)

0

0.14

112

0

0.3

47.1

1

0.72

106.9

1

0.75

44.0

2

1.36

103.4

2

1.17

41.3

3

1.88

102

3

1.36

39.4

4

2.01

101.7

4

1.61

38.8

5

2.33

101.5

5

1.87

39.6

6

2.5

101.5

6

1.96

40

7

2.6

102.3

7

2.05

40.3

8

2.67

102.6

8

2.1

40.8

9

2.63

103.6

9

2.11

41.3

10

2.65

104.2

10

2.18

42

11

2.63

104.9

11

2.2

42.2

12

2.65

105.1

12

2.27

42.7

13

2.7

105.6

13

2.36

43.6

14

2.73

106.1

14

2.45

43.8

15

2.79

106.6

15

2.5

44.5

16

2.81

107.3

16

2.51

45.2

17

2.83

107.8

17

2.57

45.9

18

2.83

108.3

18

2.59

46.5

19

2.86

108.7

19

2.55

46.7

20

2.86

109.1

20

2.55

47.2

21

2.89

109.7

21

2.57

47.8

22

2.91

110.1

22

2.56

47.8

23

2.92

110.5

23

2.57

48.1

24

2.93

110.9

24

2.55

48.6

25

2.88

111.4

25

2.56

48.9

26

2.9

111.6

26

2.48

48.9

27

2.88

112.1

27

2.49

49.6

28

2.63

112.6

28

2.45

49.9

29

2.18

112.7

29

2.4

50.3

30

1.77

113

30

2.45

50.5

31

1.42

112.8

31

2.38

50.8

32

1.12

112.4

32

1.83

51.1

33

0.88

111.9

33

1.36

51

34

0.68

110.9

34

0.92

50.4

35

0.52

109.9

35

0.58

49.3

36

0.41

108.6

36

0.32

47.3

37

0.32

107.2

37

0.19

45.2

38

0.25

105.5

38

0.11

42

IX

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

39

0.2

103.6

39

0.09

39.7

40

0.16

101.9

40

0.06

36.4

41

0.13

99.9

41

0.06

34.1

42

0.11

97.8

42

0.05

30.7

43

0.09

95.9

43

0.05

27.3

44

0.08

93.9

44

0.05

26.4

45

0.027

92

45

0.05

23.5

46

0.05

22.2

47

0.05

20.6

48

0.05

18.8

49

0.05

17.4

50

0.05

15.5

51

0.04

13.6

52

0.04

13.3

53

0.04

12.2

54

0.04

11.4

55

0.04

10.7

56

0.04

8.7

57

0.04

8.2

58

0.03

7.4

59

0.03

5.8

60

0.03

5

X

Evaluation of Deammonification process performance for supernatant treatment

Table 10A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.04.2009). 12.04.2009

R1

Time (min)

DO (mg/L)

0 1

R2 Redox (mV)

Time (min)

DO (mg/L)

Redox(mV)

0.18

-20

0.53

16.5

0

0

26.1

1

0.34

25.2

2

0.72

33.1

2

1.12

27.3

3

1.04

47.7

3

1.43

29.3

4

1.46

54.7

4

1.64

33.1

5

1.8

64.8

5

1.79

34.8

6

2.08

72.5

6

1.9

37.8

7

2.19

75.9

7

2

39.8

8

2.42

81.3

8

2.11

42.1

9

2.63

84.9

9

2.15

43.6

10

2.58

88.1

10

2.19

45.3

11

2.7

91.7

11

2.19

47

12

2.77

94.6

12

2.19

48

13

2.81

97

13

2.18

49.3

14

2.87

98.9

14

2.21

50.6

15

2.92

101

15

2.27

51.5

16

2.92

103

16

2.27

52.7

17

2.95

104.8

17

2.25

53.3

18

2.94

106.6

18

2.37

54.4

19

2.97

108.7

19

2.37

54

20

2.99

109.8

20

2.36

56

21

3

111.3

21

2.34

56.9

22

3.02

112.7

22

2.38

57.4

23

3.04

113.9

23

2.36

57.9

24

3.05

115.4

24

2.41

58.6

25

2.94

116.4

25

2.41

59.2

26

2.93

117.5

26

2.38

59.8

27

2.99

118.6

27

2.47

60.3

28

3.06

119.4

28

2.33

60.7

29

2.85

120.6

29

2.46

61.2

30

2.42

121.4

30

2.39

61.7

31

1.96

122

31

2.19

62

32

1.63

122.3

32

1.68

62.2

33

1.19

122.3

33

1.19

61.7

34

1.03

122.1

34

0.7

60.5

35

0.85

121.6

35

0.3

58.2

36

0.68

120.9

36

0.14

55.5

37

0.49

119.2

37

0.06

51.6

38

0.44

118.3

38

0.03

49.5

XI

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

39

0.38

117.4

39

0.01

45.8

40

0.32

116

40

0.01

43

41

0.27

114.2

41

0.01

40.2

42

0.24

112.7

42

0

39.7

43

0.21

110.9

43

0

32.9

44

0.19

109.1

44

0

30.2

45

0.17

107.3

45

0

27.3

46

0

25.2

47

0

22.8

48

0

20

49

0

18.3

50

0

16.7

51

0

14.7

52

0

13.2

53

0

11.7

54

0

9.4

55

0

8.7

56

0

6.1

57

0

5

58

0

4.8

59

0

3.7

60

0

2.8

XII

Evaluation of Deammonification process performance for supernatant treatment

Table 11A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.08.09). 12.08.2009 Time (min)

R1 DO (mg/L)

R2 Redox (mV)

Time (min)

0

DO (mg/L)

Redox(mV)

0

1

0.52

103.7

1

1.41

65.6

2

0.69

105.3

2

1.46

62.9

3

1.15

108.1

3

1.63

54.1

4

1.59

111.9

4

1.69

49.8

5

1.84

113.4

5

1.73

45.9

6

2.11

115.7

6

1.77

44.4

7

2.28

117.5

7

1.71

43.3

8

2.36

119.8

8

1.64

42.1

9

2.34

121.9

9

1.77

41.6

10

2.35

124.2

10

1.65

40.1

11

2.38

125.9

11

1.71

39.6

12

2.39

127.6

12

1.72

39

13

2.46

130

13

1.6

38.7

14

2.46

131.1

14

1.52

37.8

15

2.46

131.7

15

16

16

17

2.63

134.2

17

1.26

35.2

18

2.65

135.3

18

0.98

33

19

2.68

136.4

19

1.01

66.1

20

2.62

137

20

1.06

67.4

21

2.66

137.8

21

0.98

66.7

22

2.66

138.6

22

1.01

66.2

23

2.84

139.3

23

0.95

66.2

24

2.6

140

24

25

2.91

140.9

25

26

2.88

141.6

26

0.91

69.6

27

2.89

142.4

27

1.01

69.4

28

2.37

143.2

28

0.57

29

1.85

143.7

29

1

66.8

30

1.45

143.8

30

0.96

66.6

31

31

32

0.9

142.8

32

0.42

65

33

0.62

141.3

33

0.19

63.4

34

0.48

139.5

34

0.1

63.3

35

0.06

61.5

35 36

0.27

133.8

36

0.04

61

37

0.21

130.6

37

0.04

59.7

38

38

0.04

60.9

39

39

0.04

60.3

XIII

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

40

0.15

124.4

40

0.04

59.3

41

0.14

122.2

41

0.04

61.9

42

0.14

120.3

42

0.04

61.9

43

0.15

118.5

43

0.03

61.2

44

0.24

116.6

44

0.03

60.4

45

0.03

58.6

46

0.03

58.4

0.03

61.9

51

0.02

60.7

52

0.02

56.7

53

0.02

50.9

55

0.02

27.2

56

0.02

18.8

57

0.02

10.2

58

0.02

3.5

0.01

9.5

45

47 48 49 50

54

59 60

XIV

Evaluation of Deammonification process performance for supernatant treatment

Table 12A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.08.09). 12.10.2009 Time (min)

R1

R2

DO (mg/L)

Redox (mV)

Time (min)

DO (mg/L)

Redox(mV)

0

0.15

19.6

0

0.15

19.6

1

0.74

21.4

1

0.74

21.4

2

1.28

25.6

2

1.28

25.6

3

1.44

29.7

3

1.44

29.7

4

1.77

33.5

4

1.77

33.5

5

1.88

36.9

5

1.88

36.9

6

2.27

40

6

2.27

40

7

2.38

42.5

7

2.38

42.5

8

2.41

44.8

8

2.41

44.8

9

2.34

46.7

9

2.34

46.7

10

2.18

48.3

10

2.18

48.3

11

2.48

49.9

11

2.48

49.9

12

2.47

51.5

12

2.47

51.5

13

2.56

53.3

13

2.56

53.3

14

2.59

54.9

14

2.59

54.9

15

2.65

56.1

15

2.65

56.1

16

2.64

57.4

16

2.64

57.4

17

2.53

58.6

17

2.53

58.6

18

2.35

59.7

18

2.35

59.7

19

2.6

60.7

19

2.6

60.7

20

2.49

61.6

20

2.49

61.6

21

2.56

62.9

21

2.56

62.9

22

2.67

64.1

22

2.67

64.1

23

2.66

64.7

23

2.66

64.7

24

2.66

65.4

24

2.66

65.4

25

2.63

66

25

2.63

66

26

2.64

66.5

26

2.64

66.5

27

2.43

67.5

27

2.43

67.5

28

2.05

68

28

2.05

68

29

1.57

67.9

29

1.57

67.9

30

1.14

67.6

30

1.14

67.6

31

0.85

66.6

31

0.85

66.6

32

0.63

65

32

0.63

65

33

0.47

61.8

33

0.47

61.8

34

0.36

59.2

34

0.36

59.2

35

0.27

56.4

35

0.27

56.4

36

0.26

52.5

36

0.26

52.5

37

0.18

51.3

37

0.18

51.3

38

0.15

49.1

38

0.15

49.1

39

0.13

46.9

39

0.13

46.9

XV

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

40

0.13

45

40

0.13

45

41

0.11

43.2

41

0.11

43.2

42

0.11

41.8

42

0.11

41.8

43

0.11

39.8

43

0.11

39.8

44

0.1

38.2

44

0.1

38.2

0.03

61.9

51

0.02

60.7

52

0.02

56.7

53

0.02

50.9

55

0.02

27.2

56

0.02

18.8

57

0.02

10.2

58

0.02

3.5

0.01

9.5

45

45 46 47 48 49 50

54

59 60

XVI

Evaluation of Deammonification process performance for supernatant treatment

Table 13A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.14.09). 12.14.2009 Time (min)

R1

R2

DO (mg/L)

Redox (mV)

Time (min)

0

0.17

13.5

0

1

0.64

13

1

2

1.2

13.9

2

3

1.63

16.3

3

4

1.72

18.4

4

5

1.82

20.8

5

6

2.06

22.8

6

7

1.99

24.3

7

8

1.99

26.2

8

DO (mg/L)

Redox(mV)

9

2.06

27.8

9

10

2.12

28.9

10

11

2.23

29.9

11

2.89

16.7

12

2.41

30.9

12

2.63

18.8

13

2.32

31.9

13

2.81

19.8

14

2.28

32.6

14

2.92

20.9

15

2.21

33.6

15

3.05

21.9

16

2.06

34.1

16

3.14

22.8

17

2.12

34.9

17

3.26

23.6

18

2.08

32.6

18

3.19

24.2

19

2.09

33.3

19

2.54

25

20

2.1

32.5

20

3.17

25.7

21

2.08

37.1

21

3.26

26.1

22

2.13

37.6

22

3.31

26.3

23

2.2

38.8

23

3.41

27.1

24

2.22

38.4

24

3.56

27.6

25

2.25

38.7

25

3.49

28.1

26

2.29

39

26

3.43

28.7

27

2.17

39.5

27

3.4

28.7

28

1.8

39.6

28

3.38

28.9

29

1.53

39.4

29

3.34

29.1

30

1.1

38

30

3.28

29.3

31

0.91

38

31

3.27

29.5

32

0.71

36.8

32

3.05

29.8

33

0.52

35.1

33

2.52

29.4

34

0.42

33.7

34

2.21

28.9

35

0.34

31.9

35

1.86

27.9

36

0.29

30.1

36

1.53

26.6

37

0.53

28.1

37

1.22

25

38

0.22

25

38

0.98

23

39

0.2

23.3

39

0.77

20.7

XVII

13.7

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

40

0.18

20.4

40

0.61

18.2

41

0.16

18.4

41

0.47

14.9

42

0.16

17

42

0.37

11.8

43

0.15

14.8

43

0.26

7.4

44

0.14

13.2

44

0.23

4.8

45

0.14

11.8

45

0.19

1.1

46

0.14

-2.9

47

0.11

-6.2

48

0.1

-9.8

49

0.09

-12.8

50

0.08

-15.7

51

0.07

-18.4

52

0.07

-20.8

53

0.07

-23.1

54

0.07

-25

55

0.07

-27.1

56

0.07

-28.8

57

0.08

-30.3

58

0.06

-31.8

59

0.06

-33.2

60

0.05

-34.5

XVIII

Evaluation of Deammonification process performance for supernatant treatment

Table 14A. Data of Oxygen and Redox profile during intermittent aeration for one aeration/non aeration period in lab-scale Deammonification reactors (12.18.09). 12.18.2009

R1

R2

Time (min)

DO (mg/L)

Redox (mV)

Time (min)

DO (mg/L)

Redox(mV)

0

0.13

-22.6

0

0.1

-34.6

1

0.38

-21.5

1

0.35

-33

2

0.8

-18

2

1.03

-30.1

3

0.95

-14

3

1.75

-23.8

4

1.14

-10.2

4

2.12

-19.9

5

1.27

-7.1

5

2.43

-11.1

6

1.34

-4.4

6

2.69

-2.7

7

1.83

-1.9

7

2.8

-0.3

8

1.66

0.5

8

2.99

3.6

9

1.6

2.8

9

3.1

7.5

10

1.51

4.7

10

3.18

9.6

11

1.37

6.1

11

3.27

11.3

12

1.82

8

12

3.3

13.5

13

1.75

9

13

3.34

15.5

14

1.64

9.8

14

3.37

17

15

1.54

10.4

15

3.47

19.3

16

1.48

11

16

17

1.44

11.4

17

3.49

21.2

18

1.43

12.1

18

3.4

23.2

19

1.43

12.8

19

3.41

24.4

20

1.43

13.2

20

21

1.42

13.7

21

3.49

27.1

22

1.42

14.1

22

3.46

28.7

23

1.45

14.7

23

3.49

29.3

24

1.45

15.2

24

3.44

29.2

25

1.45

15.5

25

3.44

29.5

26

1.46

15.9

26

3.51

30.4

27

1.47

16.1

27

3.6

30.3

28

1.41

16.8

28

3.55

30.3

29

0.98

16.7

29

3.6

30

30

0.71

16.1

30

3.65

29.6

31

0.49

14.1

31

3.55

32.5

32

0.34

11.4

32

2.97

34.8

33

0.23

7.8

33

2.67

35.8

34

0.16

3.3

34

2.35

36.3

35

0.12

-0.5

35

1.97

36.5

36

0.09

-4.8

36

1.77

36.3

37

0.07

-8.9

37

1.5

35.5

38

0.05

-12.4

38

1.23

34.1

39

0.05

-15.5

39

1.1

32.9

XIX

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

40

0.04

-18.5

40

0.92

30.4

41

0.04

-21.2

41

0.79

28

42

0.04

-23.3

42

0.66

24.5

43

0.03

-25.5

43

0.8

19

44

0.03

-27.3

44

0.42

14.2

45

0.03

-29

45 46

0.3

7.6

47

0.26

3.9

48

0.22

0.2

0.11

-18.1

58

0.07

-29.6

59

0.06

-30.9

49 50 51 52 53 54 55 56 57

60

XX

Evaluation of Deammonification process performance for supernatant treatment

Table 15A. Data for determination of biomass attached to Kaldnes rings in lab-scale Deammonification reactor 1 (R1) during November 27st 2009 – December 21st 2009. BIOMASS Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

1

4

1.0656

1.1275

1.0729

14.70

12.96

7

4

1.0639

1.1265

1.0713

14.86

13.11

13

4

1.0578

1.1228

1.0667

15.43

13.32

22

4

1.067

1.1322

1.0741

15.48

13.79

Table 16A. Data for determination of biomass attached to Kaldnes rings in lab-scale Deammonification reactor 2 (R2) during November 27st 2009 – December 21st 2009. BIOMASS Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

1

4

1.0656

1.1275

1.0729

14.70

12.96

7

4

1.0676

1.13155

1.0769

15.18

12.97

13

4

1.0629

1.1284

1.07

15.55

13.87

22

4

1.0634

1.1291

1.0706

15.60

13.89

XXI

Evaluation of Deammonification process performance for supernatant treatment

Table 17A. Data of pressure for calculation of SAA of biomass from lab-scale Deammonification reactors during November 27st 2009 – December 21st 2009. 11.27.2009

12.03.2009

Time (min)

P (mV) R1

P(mV) R2

P (mV) R1

0

4.5

5.5

3.9

3.2

3.4

40

29.8

30

27.2

21

25.5

P(mV) R2

80

46.4

43.6

39.5

35.2

38.5

120

54.1

55.1

47.7

40.3

47.5

160

62.4

63.1

54.1

46.9

43.3

200

57.2

64.2

54.3

44.3

46.1

12.09.2009 Time (min)

P (mV) R1

12.18.2009 P(mV) R2

P (mV) R1

P(mV) R2

0

4.1

4.1

7.2

16.9

40

30

28.3

36.8

33.1

80

44.6

43.4

43.2

52.8

120

51.2

50.2

56.8

59.7

160

54.7

55.4

62.4

59.9

200

57.9

60.1

64.1

63.8

XXII

Evaluation of Deammonification process performance for supernatant treatment

A PPENDIX III. D A TA OF MEASUREMENTS AND ANALYSES FROM BATCH TESTS DURING D ECEMBER 1ST 2009 – DECEMBER 17 T H 2009. Table 18A. Data of chemical analyses by Flow Injection Analysis (FIA) for batch test no 12 (45 min aeration/15 min no aeration; DO 4mg/L). Time (min)

NH4+-N (mg/L)

NO2- -N (mg/L)

NO3- - N (mg/L)

0

157.8

0.9976

0.8494

45

133

8.148

2.452

60

127

5.88

2.978

105

101.1

9.5342

6.2858

120

95.97

6.992

6.868

165

66.98

9.6752

8.8648

180

62

6.949

9.181

225

36.08

8.935

11.955

240

30.18

5.555

12.995

Table 19A: Data of physical parameters (DO, Redox, Conductivity, pH) for batch test no 12 (45 min aeration/15 min no aeration; DO 4mg/L). Time (min)

DO (mg/L)

Redox (mV)

Conductivity (mV)

pH

1

1.77

19.20

1365.00

7.90

2

2.25

19.3

3

2.66

19.5

4

2.75

19.4

5

2.92

19.7

6

3.02

19.8

7

3.2

24.2

8

3.3

25.1

9

3.42

23.4

10

3.47

22.8

11

3.59

22.1

12

3.74

21.6

13

3.85

21.2

14

3.93

21.1

15

4.03

20.8

16

4.05

20.7

17

4.08

21

18

4.09

21.8

19

4.09

21.6

20

4.1

21.2

21

4.15

20.6

22

4.15

20.4

23

4.11

20

24

4.12

20

25

4.15

19.8

XXIII

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

26

4.11

19.7

27

4.05

19.4

28

4.03

19.5

29

4.04

19.3

30

4.01

19.4

31

4.01

19.3

32

4

19.4

33

4.05

19.4

34

4.02

19.4

35

4.01

19.6

36

4.05

19.7

37

3.98

19.8

38

4.09

19.8

39

4.08

20

40

4.03

20.1

41

3.98

20.2

42

4.08

20.4

43

4.1

20.7

44

4.09

21.1

45

4.18

21.4

46

2.87

21.8

47

2.15

21.4

48

1.44

20.5

49

0.88

18.3

50

0.67

15.7

51

0.37

13.4

52

0.25

10

53

1316.00

7.72

1204.00

7.61

8.5

54

0.17

7

55

0.11

5

56

0.08

2.8

57

0.07

1.6

58

0.06

-0.4

59

0.06

-2.1

60

0.06

-4.7

61

1.2

-3.7

62

2.15

-1.1

63

2.87

2.8

64

3.42

6.5

65

3.62

9.7

66

3.8

19.9

67

3.88

19.6

68

3.95

20.5

XXIV

Evaluation of Deammonification process performance for supernatant treatment

69

4.05

21.4

70

4.1

22.6

71

4.22

23.9

72

4.2

24.5

73

4.11

25.2

74

4

26.7

75

3.96

27.1

76

3.94

27.8

77

3.95

28.1

78

3.95

28.6

79

4

34.1

80

4.02

33.8

81

4

32.9

82

4.05

32.6

83

4.06

32.4

84

4.06

32.4

85

4.07

32.5

86

4.06

32.6

87

4.08

32.9

88

4.08

32.9

89

4.09

33.3

90

4.08

33.4

91

4.1

33.5

92

4.06

33.8

93

4.07

34

94

4.09

34.3

95

4.07

34.4

96

4.08

34.6

97

4.07

34.9

98

4.09

35.2

99

4.09

35.3

100

4.09

35.5

101

4.08

35.7

102

4.08

36

103

4.1

36.1

104

4.1

36.5

105

4.11

36.9

106

4.1

37

107

2.99

37.6

108

2.29

37.3

109

1.41

36.3

110

0.8

34.3

111

0.44

31.9

XXV

1.07

7.65

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

112

0.22

28.7

113

0.13

25.6

114

0.08

22.3

115

0.07

22.3

116

0.07

22.3

117

0.07

22.3

118

0.07

22.3

119

0.07

22.3

120

0.07

22.3

121

1.77

19.2

122

2.25

19.3

123

2.66

19.5

124

2.75

19.4

125

2.92

19.7

126

3.02

19.8

127

3.2

24.2

128

3.3

25.1

129

3.42

23.4

130

3.47

22.8

131

3.59

22.1

132

3.74

21.6

133

3.85

21.2

134

3.93

21.1

135

4.03

20.8

136

4.05

20.7

137

4.08

21

138

4.09

21.8

139

4.09

21.6

140

4.1

21.2

141

4.15

20.6

142

4.15

20.4

143

4.11

20

144

4.12

20

145

4.15

19.8

146

4.11

19.7

147

4.05

19.4

148

4.03

19.5

149

4.04

19.3

150

4.01

19.4

151

4.01

19.3

152

4

19.4

153

4.05

19.4

154

4.02

19.4

XXVI

1045.00

7.47

Evaluation of Deammonification process performance for supernatant treatment

155

4.01

19.6

156

4.05

19.7

157

3.98

19.8

158

4.09

19.8

159

4.08

20

160

4.03

20.1

161

3.98

20.2

162

4.08

20.4

163

4.1

20.7

164

4.09

21.1

165

4.18

21.4

166

2.87

21.8

167

2.15

21.4

168

1.44

20.5

169

0.88

18.3

170

0.67

15.7

171

0.37

13.4

172

0.25

10

173

0.88

7.43

0.85

7.23

8.5

174

0.17

7

175

0.11

5

176

0.08

2.8

177

0.07

1.6

178

0.06

-0.4

179

0.06

-2.1

180

0.06

-4.7

181

1.2

-3.7

182

2.15

-1.1

183

2.87

2.8

184

3.42

6.5

185

3.62

9.7

186

3.8

19.9

187

3.88

19.6

188

3.95

20.5

189

4.05

21.4

190

4.1

22.6

191

4.22

23.9

192

4.2

24.5

193

4.11

25.2

194

4

26.7

195

3.96

27.1

196

3.94

27.8

197

3.95

28.1

198

3.95

28.6

XXVII

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

199

4

34.1

200

4.02

33.8

201

4

32.9

202

4.05

32.6

203

4.06

32.4

204

4.06

32.4

205

4.07

32.5

206

4.06

32.6

207

4.08

32.9

208

4.08

32.9

209

4.09

33.3

210

4.08

33.4

211

4.1

33.5

212

4.06

33.8

213

4.07

34

214

4.09

34.3

215

4.07

34.4

216

4.08

34.6

217

4.07

34.9

218

4.09

35.2

219

4.09

35.3

220

4.09

35.5

221

4.08

35.7

222

4.08

36

223

4.1

36.1

224

4.1

36.5

225

4.11

36.9

226

4.1

37

227

2.99

37.6

228

2.29

37.3

229

1.41

36.3

230

0.8

34.3

231

0.44

31.9

232

0.22

28.7

233

0.13

25.6

234

0.08

22.3

235

0.07

22.3

236

0.07

22.3

237

0.07

22.3

238

0.07

22.3

239

0.07

22.3

240

0.07

22.3

XXVIII

0.70

7.19

0.66

6.91

Evaluation of Deammonification process performance for supernatant treatment

A PPENDIX IV. DATA OF MEASUREMENTS AND ANALYSES FROM PILOT PLANT DEAMMONIFICATION REACTOR DURING JANUARY 28ST 2009 – APRIL 2ND 2010. Table 20A. Data of physical parameters (Ph, conductivity, ORP, DO and temperature) in pilot plant Deammonification reactor during January 28st 2009 – April 2nd 2009. INFLOW Days

HRT (Days)

1

INSIDE THE REACTOR

pH

Conductivity (mS/cm)

Redox (mV)

DO (mg/L)

pH

Conductivity (mS/cm)

T (°C)

Redox (mV)

1.98

8.2

9.4708

-453

1.6

8.0

3.0308

24.9

90

2

1.98

8.3

9.3944

-533

2.0

7.7

1.4066

25.0

58

6

1.98

8.4

9.4192

-477

2.7

6.6

1.4890

24.2

155

7

1.98

8.4

9.3585

-481

1.4

6.9

1.4930

24.1

107

8

1.98

8.4

9.4047

-519

1.7

6.9

1.4996

24.0

100

9

1.98

8.3

9.2200

-508

2.0

6.8

1.8000

25.0

124

12

1.98

8.1

9.5618

-495

2.1

6.7

1.3000

24.1

101

13

1.98

8.0

9.5861

-487

1.8

6.8

1.2888

24.8

74

14

1.98

8.2

9.6150

-475

1.8

6.9

1.1925

24.1

61

15

1.98

7.8

9.5663

-470

1.9

6.9

1.2142

24.3

60

19

1.98

7.7

9.5720

-476

1.9

7.0

1.2000

24.8

66

20

1.98

7.7

9.4698

-465

2.1

7.0

1.2071

24.3

64

21

1.98

7.6

9.5400

-453

2.0

6.8

1.1900

24.9

102

22

1.98

7.7

9.5599

-480

1.5

7.1

1.2306

24.2

28

23

1.98

7.9

9.5257

-476

2.0

7.2

1.2482

24.2

30

26

1.98

7.7

9.3697

-486

3.0

6.7

1.3257

24.0

155

27

1.98

7.8

9.5112

-424

2.3

6.8

1.3149

24.8

103

28

1.98

7.7

9.3450

-491

2.1

6.8

1.3247

24.1

121

29

1.98

7.8

9.4697

-496

2.0

6.8

1.0266

24.9

165

30

1.98

7.8

9.5348

-473

2.0

6.7

1.0838

25.5

204

33

1.98

7.8

9.5784

-469

1.7

6.0

1.1368

25.2

237

XXIX

Zaira Hernando & Sandra MartĂ­nez

TRITA LWR Degree Project

34

1.98

7.7

9.5360

-453

2.1

5.9

2.0742

25.4

212

35

1.98

7.7

9.4953

-460

2.3

5.7

1.5971

25.1

206

36

2.20

7.7

9.4903

-474

1.9

6.4

1.3576

24.9

77

37

1.98

7.7

9.4550

-440

1.8

5.8

1.0638

24.5

175

40

1.98

7.5

9.5366

-485

1.5

5.6

1.5552

25.0

160

41

2.14

7.7

9.5526

-463

1.1

6.3

1.6402

25.5

127

42

1.63

7.7

9.4106

-423

1.3

7.1

1.6450

25.1

24

43

1.63

7.7

9.5059

-498

1.2

6.8

1.6760

24.9

40

44

1.63

7.8

9.2806

-488

1.2

6.6

1.5732

25.5

96

47

1.39

9.3342

-438

1.54

7.25

1.3066

25

0.31

48

1.39

9.3275

-456

1.63

7.4

1.4487

25

-11.11

49

1.39

9.6836

-474

2.21

7.44

1.4904

25

28.98

50

1.39

9.6304

-532

2.7

7.37

1.529

25

34.52

51

1.39

9.6513

-497

2.6

7.33

1.638

25

30.2

52

1.39

9.6623

-518

2.58

7.45

1.812

25

19.38

53

1.39

9.6525

-523

2.55

7.51

2.225

25

16.026

54

1.39

9.6381

-474

3.25

7.44

2.434

25.2

34.6

55

1.39

9.6597

-457

3.82

6.97

1.439

25.2

75.76

56

1.39

9.7547

-431

3.2

7.066

0.956

25.2

55.92

57

1.39

8.3

9.7422

-470

3.28

7.14

1.202

25.2

50.27

58

1.39

8.4

9.817

-511

3.44

6.97

2.637

25.2

67.09

61

1.39

8.4

9.8234

-513

3.4

7.2

2.8244

24.8

46

62

1.39

8.4

9.7035

-406

3.3

7.2

2.9103

24.5

61

63

1.39

8.4

9.8062

-539

2.9

7.1

2.6102

25.3

40

64

1.39

8.38

9.8673

-515.752

2.7646

7.07

2.4812

25.2

54.37

65

1.39

8.39

9.859

-515.5

2.764

7.03

2.404

25.2

56.52

XXX

Evaluation of Deammonification process performance for supernatant treatment

Table 21A. Data of chemical parameters (NH4+, NO3-, NO2-, alkalinity and COD) in pilot plant Deammonification reactor during January 28th 2009 – April 2nd 2009. INFLOW Days

NH4+ (mg/L)

Alkalinity (mmol/L)

COD 0.45 (mg/L)

OUTFLOW COD 1.6 (mg/L)

COD Unf. (mg/L)

NH4+

NO3-

NO2-

(mg/L)

(mg/L)

(mg/L)

Alkalinity (mmol/L)

EFFICIENCY COD 0.45 (mg/L)

COD 1.6 (mg/L)

COD Unf. (mg/L)

Nitrogen removal (%)

Ammonium removal (%)

67.81

91.13

82.82

96.86

84.53

97.22

79.17

96.77

76.50

95.51

72.19

92.51

68.31

84.25

6

1030

79.1

637

91.4

235

5.89

1.57

180

13

1020

72.8

1050

41.8

155.5

6.4

1.37

304

15

1020

72.8

1050

32

138

5.66

2.42

306

20

1030

75.2

1250

20.6

126

6.58

2.38

312

22

1030

75.2

1250

28.6

124

7.08

2.95

318

27

904

68.0

1410

35.3

122.2

5.91

1.66

340

29

904

68.0

1410

29.2

153

6.39

1.73

300

34

994

76.5

1150

44.6

180

8.96

1.18

328

328

77.1

205

4.34

1.22

318

321

163

160

5.02

7.27

380

6.83

289

302

565

73.60

91.43

3.16

358

360

587

83.93

96.28

1305

1508

36

994

76.5

1150

1305

41

1030

76.6

1280

1320

1610

43

1030

76.6

1280

1320

1610

48

1035

106.0

1154

1295

1476

50

1035

106.0

1154

55

1040

112.0

917

1040

1210

57

1040

112.0

917

1040

1210

89.1

177

8.46

58

1040

112.0

917

1040

1210

88.8

182

10.40

62

1110

79.9

696

880

1100

65

1110

79.9

696

880

1100

41.3

127

10.04

XXXI

360

Zaira Hernando & Sandra Martínez

TRITA LWR Degree Project

Table 22A. Data for determination of biomass attached to Kaldnes rings in pilot plant Deammonification reactor during January 28st2009 – April 2nd 2009. BIOMASS Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

7

4

1.0592

1.1248

1.0657

15.58

14.03

14

4

1.0649

1.1194

1.0702

12.94

11.68

20

4

1.0667

1.1206

1.0714

12.80

11.68

29

4

1.0597

1.1282

1.0661

13.06

11.74

34

4

1.0671

1.1213

1.0708

12.87

11.99

51

4

1.0686

1.1313

1.0741

14.89

13.58

55

4

1.0699

1.1382

1.0765

16.22

14.65

64

4

0.8932

0.9655

0.8992

17.17

15.74

Table 23A. Data for determination of solids in the inflow of pilot plant Deammonification reactor during January 28st2009 – April 2nd 2009. INFLOW Days

Rings

Empty plate + filter (g)

After 105 °C (g )

20

4

1.064

1.077

1.0678

0.162

0.115

29

4

1.0648

1.0734

1.0672

0.107

0.077

34

4

1.0643

1.0807

1.0675

0.205

0.165

47

4

1.0766

1.0853

1.0733

0.109

0.150

56

4

1.0534

1.063

1.0505

0.120

0.104

XXXII

After 540 °C (g)

TSS (g/L)

VSS(g/L)

Evaluation of Deammonification process performance for supernatant treatment

Table 24A. Data for determination of solids in the outflow of pilot plant Deammonification reactor during January 28st 2009 – April 2nd 2009. OUTFLOW Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

20

4

1.0695

1.081

1.071

0.144

0.125

29

4

1.0658

1.072

1.0668

0.077

0.065

34

4

1.0537

1.0935

1.0549

0.497

0.483

47

4

1.0631

1.1199

1.0786

0.710

0.516

56

4

1.0672

1.1153

1.0786

0.601

0.459

Table 25A. Data for determination of solids in activated sludge of pilot plant Deammonification reactor during January 28st2009 – April 2nd 2009. ACTIVATED SLUDGE Days

Rings

Empty plate + filter (g)

After 105 °C (g )

After 540 °C (g)

TSS (g/L)

VSS(g/L)

20

4

1.0682

1.093

1.071

0.310

0.275

29

4

1.0607

1.0875

1.065

0.335

0.281

34

4

1.069

1.1051

1.075

0.451

0.376

47

4

1.0624

1.0921

1.0639

0.371

0.353

56

4

1.0722

1.1283

1.0836

0.701

0.559

XXXIII

Evaluation of Deammonification process performance for supernatant treatment

Table 26A. Data for calculation of SAA of biomass from Pilot plant Deammonification reactor during January 28st2009 – April 2nd 2009. 02.21.2010 35 °C Time (min)

P (mV) R1

25°C P(mV) R2

P (mV) R1

P(mV) R2

0

7.5

7.9

8.7

8.1

40

26.3

32.6

23.9

26

80

45.3

49.5

30.6

35

120

53.9

59.5

35.9

44.9

160

61.3

65

40.3

47

200

69.3

67

44.8

49.7

02.26.2010 35 °C

25°C

Time (min)

P (mV) R1

P(mV) R2

P (mV) R1

P(mV) R2

0

7.5

7.9

11.2

17.5

40

26.3

32.6

20.4

30.5

80

45.3

49.5

25.5

40.9

120

53.9

59.5

35.1

48.9

160

61.3

65

42

54

200

69.3

67

65

65.1

03.03.2010 35 °C

25°C

Time (min)

P (mV) R1

P(mV) R2

P (mV) R1

P(mV) R2

0

7.9

8.6

9.8

8.8

40

27.2

21.3

19.8

13.6

80

48.3

45

26

14.8

120

56.5

59

32.8

16

160

62

69

38.1

17.5

40.6

18.5

200

3.08.2010 35 °C

25°C

Time (min)

P (mV) R1

P(mV) R2

P (mV) R1

P(mV) R2

0

9

10.9

9.7

8.94

40

34.9

27.5

26.8

30.1

80

50.8

51.8

34.8

36.1

120

55.5

59.9

44.4

49.1

160

72.2

68.7

200

79

73.5

XXXIV

Evaluation of Deammonification process performance for supernatant treatment

03.18.2010 35 째C

25째C

Time (min)

P (mV) R1

P(mV) R2

0

12.7

10.6

9

8.4

40

26.6

27.3

24.8

28.1

80

43.8

44.9

32.8

35.1

120

44.6

53.6

41.4

47.1

160

P (mV) R1

P(mV) R2

66.7

200

03.28.2010 35 째C

25째C

Time (min)

P (mV) R1

P(mV) R2

0

11.6

9.9

10.1

9.9

40

45.4

49.8

23

24.6

80

57.8

66.9

35.3

39.9

120

54.7

73.1

39.5

47.5

160

71

75.1

P (mV) R1

200

XXXV

P(mV) R2